Method of manufacturing a component of an outsole for use in an article of footwear

ABSTRACT

An outsole component for use in an article of footwear is manufactured using a molding process that incorporates a second polymeric material with a film component including a first layer formed of a polymeric hydrogel material. The first layer forms the external or ground-facing layer of the outsole. Methods of manufacturing the outsole component, as well as articles of footwear including outsole component and methods of manufacturing such articles of footwear are also described.

This application claims priority to U.S. Provisional Application No.62/539,720 filed on Aug. 1, 2017, the entire contents of which areincorporated herein by reference.

FIELD

This disclosure relates generally to articles of footwear. Morespecifically, the present disclosure relates to the manufacture ofcomponents of outsoles which can include complete outsole units that canbe incorporated into articles of footwear such as those that are usedunder conditions conducive to the accumulation of soil on the outsoles.

BACKGROUND

The statements in this section merely provide background informationrelated to the present disclosure and may not constitute prior art.

Articles of footwear of various types are frequently used for a varietyof activities including outdoor activities, military use, andcompetitive sports. The outsoles of these types of footwear often aredesigned to provide traction on soft and slippery surfaces, such asunpaved surfaces including grass and dirt. For example, exaggeratedtread patterns, lugs, cleats or spikes (both integral and removable),and rubber formulations which provide improved traction under wetconditions, have been used to improve the level of traction provided bythe outsoles.

While these conventional means generally help give footwear improvedtraction, the outsoles often accumulate soil (e.g., inorganic materialssuch as mud, dirt, sand and gravel, organic material such as grass,turf, and other vegetation, and combinations of inorganic and organicmaterials) when the footwear is used on unpaved surfaces. In someinstances, the soil can accumulate in the tread pattern (when a treadpattern is present), around and between lugs (when lugs are present), oron shafts of the cleats, in the spaces surrounding the cleats, and inthe interstitial regions between the cleats (when cleats are present).The accumulations of soil can weigh down the footwear and interfere withthe traction between the outsole and the ground.

DRAWINGS

In order that the disclosure may be well understood, there will now bedescribed various forms thereof, given by way of example, referencebeing made to the accompanying drawings, in which:

FIG. 1 is a flowchart describing a method of manufacturing an outsole ora component of an outsole according to an aspect of the presentdisclosure;

FIG. 2A is a bottom side view of various components of an outsole formedaccording to an aspect of the present disclosure;

FIG. 2B is a bottom side view of various components of an outsole formedaccording to an aspect of the present disclosure;

FIG. 3A is a bottom side view of the external surface of an outsole withtraction elements according to an aspect of the present disclosure;

FIG. 3B is a perspective view of an article of footwear having anoutsole with traction elements according to an aspect of the presentdisclosure;

FIG. 3C is a bottom side view of the external surface of the outsolehaving traction elements according to an aspect of the presentdisclosure;

FIG. 3D is a perspective view of an article of footwear having anoutsole with traction elements according to an aspect of the presentdisclosure; and

FIG. 4 is a flowchart describing a method of manufacturing an article offootwear that includes an outsole formed according to an aspect of thepresent disclosure.

The drawings described herein are for illustration purposes only and arenot intended to limit the scope of the present disclosure in any way.

DETAILED DESCRIPTION

The present disclosure generally provides an improved manufacturingprocess for making outsole components using a polymeric hydrogelmaterial, as well as the outsole component formed therefrom.

Previous methods of manufacturing an outsole component for an article offootwear which include a hydrogel material defining a ground-contactingsurface of the component involved first conforming a substantiallyplanar portion of a hydrogel film to the curved shape of an outsoleusing a thermoforming process by heating and drawing the film against amold, forming a curved and shaped film component having athree-dimensional shape (e.g., a curved and shaped component, thecomponent having a depth at least 5 times greater than a thickness ofthe hydrogel film prior to the thermoforming). Due to the configurationof thermoforming equipment, a relatively large portion of the film isfed into the equipment (e.g., a 9 inch by 16 inch portion of film) tothermoform a single component, leading to a large proportion of theportion of film being wasted as scrap, After cooling the curved, shapedfilm component, excess film was then trimmed from a curved region of theperimeter of the curved, shaped film component. The trimmed componentwas then placed in an injection mold, and the mold was then backinjected with a thermoplastic material to form the outsole component.This process required heating the hydrogel film twice—first during thethermoforming step, and then during the back-injection step. Thisprocess also involved drawing the hydrogel film while it was heatedduring the thermoforming process, producing thinning of the film in someregions of the component, such as in regions on or between tractionelements, as well as a large proportion of excess material which endedup as scrap. Additionally, this process also required trimming theexcess material from the perimeter of the thermoformed portion, in anarea that was curved (i.e., not substantially planar), requiring eithermanually cutting out each thermoformed component, or using complicated,slow and expensive automated cutting equipment capable of cutting in thex, y and z dimensions.

In contrast, the present method eliminates the need for thethermoforming step. Eliminating the thermoforming step reduces thethermal history to which the hydrogel material is exposed duringmanufacturing, which can lead to reduced defects and increaseddurability in the finished product. The present method can also reducethe amount of scrap material produced while allowing the use of simpler,faster, more cost-effective manufacturing processes which can be morereadily automated.

In one aspect, the present disclosure is directed to a method ofmanufacturing an outsole component for an article of footwear, themethod comprising: providing a film component comprising a firstexternally-facing surface, the film component including a first layercompositionally comprising a polymeric hydrogel material, the firstlayer defining at least a portion of the first externally-facing surfaceof the film component; providing a mold having a molding surface;placing the film component into the mold; restraining the film componentso that at least a portion of the first layer against the portion of themolding surface, forming a restrained film component; charging a secondpolymeric material into the mold with the restrained film component; atleast partially solidifying the charged second polymeric material in themold to produce an outsole component with an outermost surfacecomprising at least a portion of the first layer of the film component;and removing the outsole component from the mold. The present disclosureis also directed to outsole components manufactured according to thesemethods, as well as methods of manufacturing articles of footwearcomprising providing an outsole component manufactured according tothese methods, providing an upper for an article of footwear, andsecuring the outsole component and the upper to each other, such thatthe polymeric hydrogel material of the outsole component defines aground-facing surface of the article of footwear.

In another aspect, the present disclosure is directed to an outsolecomponent for an article of footwear, the outsole component comprising:a ground-contacting surface; at least one film component, the filmcomponent having a first surface, a second surface opposed to the firstsurface, and an external perimeter, the film component compositionallycomprising a polymeric hydrogel material, the polymeric hydrogelmaterial defining at least a portion of the first surface of the filmcomponent, and at least a portion of a ground-contacting surface of theoutsole component; a second polymeric material operably connected to thesecond surface of the film component and to the entire externalperimeter of each of the one or more film components; and one or moretraction elements; wherein the at least one film component fits betweenor around the one or more traction elements.

Now having describe aspects of the present disclosure generally,additional details are provided. In an aspect, the method of the presentdisclosure begins with providing a film component including a firstlayer comprising a polymeric hydrogel material. Instead of providing aportion of hydrogel film, thermoforming the portion into athree-dimensional curved shape and then trimming along a perimeter ofthe thermoformed region to form a component which will fit within aninjection mold, in the present method, the hydrogel film is provided asa film component. The film component is configured to be placed into amold, i.e., when the mold is closed, the film component does not extendbeyond the perimeter of the molding surface of the mold. The filmcomponent can be a pre-cut component, such as a substantially planarpre-cut film component. In particular aspects, once the film of the filmcomponent has been formed, the film itself as well as the film componentare not thermoformed or otherwise heated above 80° C.

In some aspects, a portion of film can be cut or stamped or molded toform the shape of the film component. The film can be an extruded orco-extruded film, including an extruded layered film. In some aspects,the film component is configured to fit between or around one or moretraction elements; i.e., the perimeter of the film component can beshaped to go between or around the base of a traction element, or one ormore interior portions of the film component can be cut out e.g.,forming a hole or a void, to go between or around the base of one ormore traction elements, or both.

Next, a mold having a molding surface is provided, and the filmcomponent is placed in the mold so that a portion of the first layer ofthe film component (the first layer comprising the polymeric hydrogelmaterial) contacts a portion of the molding surface of the mold. Inaspects where the film component is substantially planar and the moldingsurface is curved, the film component can be bent or curved in order tofit into the mold and contact the molding surface. However, it is to beunderstood that this bending or curving will not involve heating thefilm component above 80 degrees Celsius (C). Next, the portion of thefirst layer contacting the molding surface is restrained against theportion of the molding surface while a second polymeric material ischarged into the mold. Restraining the portion of the first layeragainst the molding surface reduces or eliminates the need to thermoformthe film component and can prevent or reduce seepage of the secondpolymeric material between the film component and the molding surfaceduring the charging step. In some aspects, the step of restraining thefirst layer of the portion against the molding surface can includeapplying a vacuum to the film component, or applying pins to the filmcomponent, or both. The charging step can include injection molding orpouring the second polymeric material into the mold. Once the secondpolymeric material has at least partially solidified within the mold,the outsole component can be removed from the mold. The use of theprocess of this disclosure avoids issues such as drawing and stretchingof the film during thermoforming, which can damage the film resulting inrejects or scrap. The use of this process also reduces the “thermalhistory” of the film by limiting the number of times the hydrogelmaterial is exposed to temperatures above 80 degrees C. during themanufacturing process, which can result in degradation of the material.The use of this process can also reduce the amount of waste material ascompared to a conventional thermoforming process.

As used herein the term “outsole component” refers to a component whichcan be combined with one or more additional components to form acomplete outsole unit, as well as to a complete outsole unit which canbe attached to an upper to form an article of footwear. The termpolymeric hydrogel material, hydrogel material, and hydrogel are usedinterchangeably throughout the disclosure to refer to the same elementor material composition.

According to one aspect of a method of manufacturing an outsolecomponent for an article of footwear according to the present disclosurecomprises providing one or more flat film components that are formed ofa layered film having a polymeric material forming a backing layer and apolymeric hydrogel material operably connected to the backing layer,such that the polymeric hydrogel material defines an externally-facingsurface of the flat film component. Then a mold having a molding surfaceis provided and the flat film component is placed into the mold suchthat the polymeric hydrogel layer of the layered film is in directcontact with at least a portion of the molding surface. A secondpolymeric material is added into the mold such that the film componentdefines at least a portion of an external surface of the outsole withthe hydrogel forming an outermost layer thereof. The film component isheld against the molding surface during at least a portion of the addingof the second polymeric material to the mold. The second polymericmaterial is solidified in the mold; and the outsole or outsole componentis then removed from the mold.

According to another aspect of the present disclosure, a method ofmanufacturing an article of footwear comprises providing an outsolecomponent manufactured according to the method described above andfurther defined herein; providing an upper; and securing the outsolecomponent and the upper to each other, such that the polymeric hydrogelmaterial defines a ground-facing surface of the article of footwear.

According to yet another aspect of the present disclosure an outsolecomponent for an article of footwear comprises one or more filmcomponents, wherein each of the film components has an externalperimeter and the film of each of the film components comprises abacking layer of a first polymeric film and a polymeric hydrogelmaterial operably connected to the backing layer, such that thepolymeric hydrogel material defines a ground-contacting surface of theoutsole component. A second polymeric material is operably connected tothe backing layer and to the entire external perimeter of each of theone or more film components. The outsole component further comprises oneor more traction elements with the one or more film components beingconfigured to fit between or around the traction elements.

The outsole components formed according to the teachings of the presentdisclosure can prevent or reduce the accumulation of soil on theirsurfaces during use or wear on unpaved surfaces. As used herein, theterm “soil” includes one or more of a variety of materials that arecommonly present in the ground or on playing surfaces, which mightotherwise adhere to an article (e.g., exposed outsole of a footweararticle, etc.). Soil can include, without limitation, inorganicmaterials, such as mud, sand, dirt, and gravel; organic matter such asgrass, turf, leaves, other vegetation, and excrement; and combinationsof inorganic and organic materials, such as clay. Additionally, soil caninclude other materials such as pulverized rubber which may be presenton or in an unpaved surface.

As one skilled in the art will appreciate, preventing or reducing soilaccumulation on articles of footwear can provide many benefits.Preventing or reducing soil accumulation on the outsoles of articles offootwear during wear on unpaved surfaces also can significantly affectthe weight of accumulated soil adhered to the outsole during wear,reducing fatigue to the wearer caused by the adhered soil. Preventing orreducing soil accumulation on the outsole can help preserve tractionduring wear. For example, preventing or reducing soil accumulation onthe outsole can improve or preserve the performance of traction elementspresent on the ground-facing surface of the outsole during wear onunpaved surfaces. When worn while playing sports, preventing or reducingsoil accumulation on outsoles can improve or preserve the ability of thewearer to manipulate sporting equipment such as a ball with the articleof footwear. Further, preventing or reducing soil accumulation on theoutsole can make it easier to clean the article of footwear followinguse.

The following description is merely exemplary in nature and not intendedto limit the present disclosure or its application or uses. For example,the outsole or component of an outsole incorporated in the articles offootwear, as made and used according to the teachings contained herein,is described throughout the present disclosure in conjunction withseveral examples of tread patterns and traction elements in order tomore fully illustrate the composition and the use thereof. Theincorporation and use of such an outsole or component of an outsole inarticles of footwear with different tread patterns and traction elementsare within the scope of the present disclosure. One skilled in the artwill understand that throughout the description, corresponding referencenumerals indicate like or corresponding parts and features. Furtherareas of applicability will become apparent from the descriptionprovided herein.

As used herein, the terms “article of footwear” and “footwear” areintended to be used interchangeably to refer to the same article.Typically, the term “article of footwear” will be used in a firstinstance, and the term “footwear” can be subsequently used to refer tothe same article for ease of readability.

The outsoles or components of outsoles for use in an article of footwearmanufactured according to the teachings of the present disclosure can bedesigned for a variety of uses, such as sporting, athletic, military,work-related, recreational, or casual use. For example, an article offootwear can be intended for outdoor use on unpaved surfaces (in part orin whole), such as on a ground surface that includes one or more ofgrass, turf, gravel, sand, dirt, clay, mud, and the like. The surfacecan be a general outdoor surface or an athletic performance surface(e.g., football/soccer field, golf course, baseball field, running trackand field, cycling course, etc.). The article of footwear can beintended for indoor use, such as in indoor sports that are played upondirt surfaces (e.g., indoor baseball fields with dirt infields andindoor football/soccer pitches). These articles of footwear canoptionally include traction elements (e.g., lugs, cleats, studs, spikes,etc.) to provide traction on soft and slippery surfaces. Cleats, studsand spikes are commonly included in footwear designed for use in sports,such as football/soccer, golf, baseball, and the like, which arefrequently played on unpaved surfaces. Lugs and/or exaggerated treadpatterns are commonly included in footwear including boots design foruse under rugged outdoor conditions, such as trail running, hiking, andmilitary use.

Referring to FIG. 1, the method of manufacturing 1 an outsole componentfor use in an article of footwear comprises providing 5 a flat filmcomponent that includes a first layer compositionally comprising,consisting of, or consisting essentially of a polymeric hydrogelmaterial defining an externally-facing surface of the flat filmcomponent. The polymeric hydrogel material represents a first polymericmaterial used in the process. The method of manufacturing 1 furthercomprises providing 10 a mold with a molding surface. This moldingsurface can have a predetermined shape for the desired outsolecomponent. The flat film component is placed 15 into the mold such thata portion of the first layer contacts a portion of the molding surface.When necessary or desirable, the flat film component can be bent orcurved 13 such that it conforms to a curvature associated with themolding surface while maintaining the film component at a temperature inthe range of about 10 degrees C. to about 80 degrees C.

According to the method of manufacturing 1, a portion of the first layeris restrained or held against a portion of the molding surface whilecharging a second polymeric material 20 into the mold such that the filmcomponent defines at least a portion of the first layer of the filmcomponent forms an outermost layer of the outsole component. The filmcomponent is held 20 against the molding surface during at least aportion of the adding of the second polymeric material to the mold. Thefilm component can be held in place using a holding mechanism. Thesecond polymeric material is allowed to at least partially solidify 25to produce the outsole component with a portion of the first layer asthe outermost layer. Then the outsole component that is formed isremoved 30 from the mold. The molding steps 20, 25 can be accomplished,without limitation, within the confines of an injection molding orcompression molding process.

The step of placing the film component into the mold 15 so that aportion of the first layer contacts a portion of the molding surfacecomprises placing the film component into the mold so that the firstlayer contacts a portion of the molding surface that is less than 85percent of the total molding surface area of the mold. Alternatively,the first layer contacts a portion of the molding surface that is lessthan 80 percent; alternatively, less than 75 percent; alternatively,between about 10 percent and about 80 percent of the total moldingsurface area of the mold.

As used herein, the total molding surface area corresponds to thesurface area(s) of a section(s) of the mold against to which the layeris restrained. For example, the total surface area for a two-pieceinjection mold represents the total surface area of half the mold whenthe film component is restrained or held against that half of the moldduring the molding operation.

In this method of manufacturing 1, the molding steps 20, 25 associatedwith forming the outsole component are the only steps in the method ofmanufacturing 1 that potentially exposes the hydrogel to a thermaltreatment. In other words, the flat film component is maintained at atemperature in the range of about 10 degrees C. to about 80 degrees C.during the method of manufacturing 1, except during the step of charging20 the second polymeric material into the mold including followingcharging the second polymer material into the mold and at leastpartially solidifying the second polymeric material in the mold 25.

The step of charging the mold 20 with the second polymeric material intothe mold can include closing the mold and injecting the second polymericmaterial into the closed mold using an injection molding process. Thestep of charging the mold 20 can also include charging the secondpolymeric material into the mold, closing the mold before, during, orafter the charging, and applying compression to the closed mold.

Although the layered film is described in the method of manufacturing 1as being a flat component, the layered film can be substantially planaror relatively planar with some degree of curvature in a portion of theflat component or along one or more edges of the flat component. Agreater degree of curvature can be incorporated into the flat component,for example during the molding steps 20, 25 as further defined herein.When desirable, the flat film component can optionally be bent or curvedto conform to a curvature of the molding surface 13.

According to various aspects of the present disclosure, the flat filmcomponent can be formed by an extrusion process, or a co-extrusion or alamination process 2. When desirable, the film component can comprise abacking layer formed of a third polymeric material 8. The flat filmcomponent can be prepared by providing 3 the third polymeric material;providing 7 the polymeric hydrogel material; and forming the layeredfilm by a co-extrusion or lamination process 9 to provide a filmcomponent having a polymeric hydrogel layer and backing layer comprisingthe third polymer. The polymeric hydrogel can be exposed to a thermaltreatment that exceeds 80 degrees C. during the extrusion, co-extrusionor lamination process used to form the layered film. Thus, in this case,the flat film component is maintained at a temperature in a range ofabout 10 degrees C. to about 80 degrees C. except during the steps offorming the layered film 2, 9, adding the second polymeric material intothe mold 20 and after charging the mold with the second polymericmaterial, and at least partially solidifying the second polymericmaterial in the mold 25.

When desirable, the third polymeric material can be at least partiallycured 6, or alternatively, fully cured prior to being used in theoutsole method of manufacturing 1 or during the molding steps 20, 25 inthe process. However, the flat film component is not subjected to anyother process steps during the manufacturing process 1, such asthermoforming or vacuum forming that exposes the flat component to anelevated temperature (i.e., a thermal treatment) capable of forming theflat component into a curved shape.

As used herein, the term “providing”, such as for “providing anoutsole”, when recited in the claims, is not intended to require anyparticular delivery or receipt of the provided item. Rather, the term“providing” is merely used to recite items that will be referred to insubsequent elements of the claim(s), for purposes of clarity and ease ofreadability.

Still referring to FIG. 1, the method of manufacturing 1 can furthercomprise at least partially curing 29 the second polymeric material.When desirable the second polymeric material can be fully cured. For thepurpose of this disclosure, the term “partially cured” denotes theoccurrence of at least about 1 percent, alternatively, at least about 5percent of the total polymerization required to achieve a substantiallyfull cure. The term “fully cured” is intended to mean a substantiallyfull cure in which the degree of curing is such that the physicalproperties of the cured material do not noticeably change upon furtherexposure to conditions that induce curing (e.g., temperature, pressure,presence of curing agents, etc.).

For the purpose of this disclosure, the terms “about” and“substantially” are used herein with respect to measurable values andranges due to expected variations known to those skilled in the art(e.g., limitations and variability in measurements).

Still referring to FIG. 1, the layered film can be cut 11 in order toform a flat film component that is configured to fit between or aroundone or more traction elements. When desirable, a portion of the layeredfilm can be configured 16 to fit between or around one or more tractionelements by cutting one or more holes or voids into the portion of thefilm to accommodate the traction elements, or by shaping the portion ofthe film to avoid the one or more traction elements, or by both cuttingand shaping the film. One skilled in the art will understand the variousway or methods in which a layered film can be cut. One aspect, ofcutting the layered film is, without limitation, through the use of adie cutting operation using a flatbed press or a rotary press. Diecutting can be accomplished using a solid engraved die, an adjustabledie, magnetic plate tooling, a dinking die, or a combination thereof.

Referring now to FIGS. 2A and 2B, a layered film of the flat filmcomponent 50 is shown after cutting 11 in the method of manufacturing 1of FIG. 1. The cutting step can be configured to provide one or moreholes or voids (e.g., 55, 60) that fit around one or more tractionelements and provide a substantially contiguous region of the flat filmalong at least a portion of the outsole of the footwear. For example,referring to FIG. 2B, one or more holes 55 can be cut or punched intothe flat film, each hole 55 having a shape and size to accommodate acorresponding traction element, so that, for example, the tractionelement can extend through the hole 55, or project from the outsole in aregion substantially corresponding to the hole 55 in the film. Referringto FIG. 2A, one or more contours or voids 60 can be formed at or nearthe edges of the formed film, each contour or void 60 having a shape andsize to accommodate a corresponding traction element, so that, forexample, the traction element can project from the outsole in a regionsubstantially corresponding to the void 60 in the film. In addition,configuring the film to fit between or around the traction elements cancomprise cutting one or more holes in the flat portion to accommodatethe traction elements or shaping the flat portion to avoid the tractionelements. According to these aspects, the traction elements of theoutsole do not comprise any of the hydrogel material.

Referring once again to FIG. 1, the mold provided in step 10 for use inthe injection molding steps 20, 25 can include a molding surface ofwhich at least a portion thereof is curved into a predetermined shape.The desired shape of the outsole or the component of the outsole to beformed defines the degree of curvature associated with the moldingsurface. Thus, the molding surface is in the predetermined shape of theoutsole component that is to be formed.

A portion of the first layer of the flat film component can berestrained or held 20 against the molding surface using a holdingmechanism that can include, but not be limited to, vacuum, one or moreretractable pins, or a combination thereof. During the molding steps 20,25 at least a portion of the first layer of the flat film component isplaced against the molding surface 15, such that after the addition ofthe second polymeric material and cooling or solidifying 25 thereof, thelayered film assumes the shape of the molding surface. In thisconfiguration, the polymeric hydrogel material in the first layer of theflat film component forms at least a portion of the external surface ofthe outsole. According to some aspects, the polymeric hydrogel materialforms at least 80%, or at least 85%, of the external surface of theoutsole component.

Referring once again to FIGS. 2A and 2B, various aspects of an outsolecomponent 65 formed via the method of manufacturing 1 are illustrated toshow the incorporation of the flat film component 50 into the outsolecomponent 65. As illustrated, the outsole component 65 has severaltraction elements 70 formed therewith. The traction elements can beintegrally formed with the outsole during the molding steps 20, 25. Inthis case, the traction elements are substantially comprised of thesecond polymeric material or a third polymeric material. According tothese aspects, the flat film component 50 has been configured tocomprise holes or voids 55, 60, that correspond to the location of saidtraction elements 70, so that the traction elements 70 extend through orfrom regions of the outsole component 65 that correspond to the locationof the holes or voids 55, 60 (i.e., the regions that lack the hydrogelmaterial).

Referring once again to FIG. 1, when desirable, a fourth polymericmaterial can be added 27 to the mold from which at least a portion ofthe traction elements are formed. Alternatively, in some aspects all ofthe traction elements can be formed from the fourth polymeric material.The fourth material can be at least partially cured 29 when desirable.The fourth polymeric material can be a thermoplastic polymeric material.When desirable, the fourth polymeric material can be of the same orsimilar composition as the second or third polymeric materials. Thefourth polymeric material can exhibit a greater degree of abrasionresistance than the second or third polymeric materials.

According to some aspects, one or more of the traction elements cancomprise an element that is added separately after the outsole isremoved from the mold, for example, as snap-fit, screw-on components, ora combination thereof. In these aspects, the separately-added tractionelements can be individually selected to comprise the same material asthe second, third, or fourth polymeric materials or a material that isdifferent than or substantially free of the second, third, or fourthpolymeric materials. The separately-added traction elements can bepermanently or removably coupled with the outsole. When desirable, asshown in FIG. 1, one or more fittings can be placed 17(A) into the moldprior to adding the second polymeric material in order to be formed withthe outsole or the outsole component. These fittings are configured tocouple with the separately-added traction elements, e.g., snap-fit orscrew-on components. According to certain aspects, preformed tractionelement tips can be placed 17(B) into the mold prior to adding thesecond polymeric material in order to be formed with the outsole or theoutsole component. These pre-formed traction elements can beindividually selected to comprise the same material as the second,third, or fourth polymeric materials or a material that is differentthan or substantially free of the second, third, or fourth polymericmaterials.

Referring now to FIGS. 3A-3D, the one or more traction elements 70provided on the external surface 75 of the outsole 65 can represent atread pattern, lugs, cleats, studs, spikes, or a combination thereof.The number of traction elements 70 and the location or pattern of thetraction elements located on the ground-facing or external surface 75 ofthe outsole 65 can vary between different articles of footwear 80. Thelocation and pattern of the traction elements can be predetermined toprovide a necessary or desired effect or function.

According to another aspect of the present disclosure, an outsolecomponent for an article of footwear comprises one or more filmcomponents, wherein each of the film components has an externalperimeter and the film of each of the film components comprises abacking layer of a first polymeric film and a polymeric hydrogelmaterial operably connected to the backing layer, such that thepolymeric hydrogel material defines a ground-contacting surface of theoutsole component. A second polymeric material is operably connected tothe backing layer and to the entire external perimeter of each of theone or more film components. The outsole component further comprises oneor more traction elements with the one or more film components beingconfigured to fit between or around the traction elements. The tractionelements can have a ground-contacting surface that does not include thefilm component. The film component can include a void having an interiorperimeter, and the traction elements passes through the void of the filmcomponent. When desirable, the traction element can comprise the secondpolymeric material, which is operably connected to the interiorperimeter of the film component. The second polymeric material can alsodefine the ground-contacting surface of the traction element.

The outsole 65 can be incorporated into an article of footwear 80 (bestshown in FIGS. 3B and 3D), such that the outsole 65 is coupled with orattached to an upper 85. The upper 85 of the footwear 80 has a bodywhich can be fabricated from materials known in the art for makingarticles of footwear, and is configured to receive a user's foot. Theupper 85 of a shoe 85 consists of all components of the shoe above theoutsole 65. The different components of the upper 85 can include a toebox; heal counter; and an Achilles notch, to name a few. Thesecomponents can be attached by stitches or more likely molded to become asingle unit to which the outsole 65 is coupled.

Referring now to FIG. 4, according to another aspect of the presentdisclosure, a method of forming an article of footwear 100 can comprise,consist of, or consist essentially of providing or receiving 105 anupper; providing or receiving 110 an outsole component that ismanufactured according the method of manufacturing 1 as previouslydescribed and further defined herein; and coupling or securing 115 theupper and the outsole component together. When desirable, the method canfurther include receiving 120 a midsole; and coupling 125 the midsole tooutsole component and/or the upper prior to the coupling of the outsolecomponent to the upper, such that the midsole resides between theoutsole component and the upper.

The method of forming an article of footwear 100 can also comprise atleast partially curing 130 the second, third, and/or fourth polymericmaterials that are used in manufacturing the outsole through theoccurrence of one or more cross-linking mechanisms. The occurrence ofsuch cross-linking mechanisms can occur, for example, via a sulfur-basedcross-linking process or a peroxide-initiated cross-linking processresulting in the curing of the polymeric materials or by exposing thepolymeric materials to actinic radiation at a concentration and for aduration to at least partially cure the mixture.

When desirable, the method of forming an article of footwear 100 canalso utilize an adhesive, primer, or a combination of both 135 to assistin securing or attaching the outsole component to the upper and/or themidsole to the upper or outsole. The adhesive or primer can comprise,but not be limited to, an epoxy, urethane, acrylic, cyanoacrylate,silicone, or a combination thereof.

While not wishing to be bound by theory, it is believed that the outsoleof the article of footwear formed according to the present disclosure,when sufficiently wetted with water (including water containingdissolved, dispersed or otherwise suspended materials) can providecompressive compliance and/or expulsion of up taken water. Inparticular, it is believed that the compressive compliance of the wetsurface composition of the component, the expulsion of liquid from thewet surface composition, or a combination thereof, can disrupt theadhesion of soil to the component of the article and/or cohesion of thesoil particles to each other.

This disruption in the adhesion and/or cohesion of soil is believed tobe a mechanism capable of preventing (or otherwise reducing) the soilfrom accumulating on the outsole (due to the presence of the wetmaterial), or at least allows the soil to be removed with less effort(e.g., easier to wipe, brush, or otherwise physically remove). As oneskilled in the art will appreciate, the prevention of soil fromaccumulating on the outsoles can provide numerous benefits, such aspreventing weight accumulation on the articles of footwear.

As discussed above, the external surface of the outsole componentmanufactured by the method of the present disclosure includes apolymeric hydrogel material that allows the material to take up water.As used herein, the terms “take up”, “taking up”, “uptake”, “uptaking”,and the like refer to the drawing of a liquid (e.g., water) from anexternal source into the component, such as by absorption, adsorption,capillary action or a combination thereof. Furthermore, as brieflymentioned above, the term “water” refers to an aqueous liquid that canbe pure water, or can be an aqueous carrier with lesser amounts ofdissolved, dispersed or otherwise suspended materials (e.g.,particulates, other liquids, and the like).

The ability of the polymeric hydrogel material to take up water andswell along with an associated increase in compliance can reflect itsability to prevent soil accumulation during use of the article offootwear. For the sake of convenience the polymeric hydrogel materialcan be described hereafter using the general term “hydrogel”. Asdiscussed above, when the hydrogel takes up water (e.g., throughabsorption, adsorption, capillary action, etc.), the water taken up bythe hydrogel transitions the hydrogel from a dry, relatively more rigidstate to a partially hydrated or fully saturated state that isrelatively more compliant. The presence of water at the surface of thehydrogel is believed to be one mechanism that reduces the adherence ofsoil to the material.

Additionally, when a hydrated hydrogel is subjected to an application ofpressure, either compressive or flexing, the hydrogel can reduce involume, and expel at least a portion of its uptaken water. This expelledwater is believed to reduce or disrupt the adhesive/cohesive forces ofsoil particles on or at the surface of the outsole. In particular, it isbelieved that the compressive compliance of the hydrated hydrogelmaterial, the expulsion of liquid from the hydrated hydrogel material,or both in combination, can disrupt the adhesion of soil on or at theoutsole, or the cohesion of the particles to each other, or can disruptboth the adhesion and cohesion. This disruption in the adhesion and/orcohesion of soil is believed to be a responsible mechanism forpreventing (or otherwise reducing) the soil from accumulating on thefootwear outsole (due to the presence of the wet material). As can beappreciated, preventing soil from accumulating on the bottom of footwearcan improve the performance of traction elements present on the outsoleduring wear on unpaved surfaces, can prevent the footwear from gainingweight due to accumulated soil during wear, can preserve ball handlingperformance of the footwear, and thus can provide significant benefitsto wearer as compared to an article of footwear without the materialpresent on the outsole. Accordingly, the material can undergo dynamictransitions, and these dynamic transitions can result in forces orconditions that dislodge accumulated soil or otherwise reduce soilaccumulation on the article as well.

The total amount of water that the hydrogel can take up depends on avariety of factors, such as its composition (e.g., its hydrophilicity),its cross-linking density, its thickness, and the existence and/orinterfacial bond to other materials, such as the third polymericmaterial present as a backing layer in the layered film. For example, itis believed that a hydrogel comprising a polymeric network having ahigher level of hydrophilicity and a lower level of cross-linkingdensity can increase the water uptake capacity of the hydrogel. On theother hand, the interfacial bond between the hydrogel and a thirdpolymeric material as a backing layer in the layered film canpotentially restrict the swelling of the hydrogel. Accordingly, asdescribed below, the water uptake capacity and the swelling capacity ofthe hydrogel can differ between the hydrogel in a neat film state(isolated film by itself) and the hydrogel as present the layered film.

The water uptake capacity and the water uptake rate of the hydrogel alsocan be dependent, at least in part, on the size and shape of itsgeometry, and are typically based on the same factors. However, it hasbeen found that, to account for part dimensions when measuring wateruptake capacity, it is possible to derive an intrinsic, steady-statematerial property. Therefore, conservation of mass can be used to definethe ratio of water weight absorbed to the initial dry weight of thehydrogel at very long timescales (i.e. when the ratio is no longerchanging at a measurable rate).

Conversely, the water uptake rate is transient and can be definedkinetically. The three primary factors for water uptake rate for ahydrogel present at a surface of an outsole given part geometry includetime, thickness, and the exposed surface area available for taking upwater. Once again, the weight of water taken up can be used as a metricof water uptake rate, but the water flux can also be accounted for bynormalizing by the exposed surface area. For example, a thin rectangularfilm can be defined by 2×L×W, where L is the length of one side and W isthe width. The value is doubled to account for the two major surfaces ofthe film, but the prefactor can be eliminated when the film has anon-absorbing, structural layer secured to one of the major surfaces(e.g., with an outsole backing plate of the third polymeric material inthe layered film).

In addition to swelling, the compliance of the polymeric hydrogelmaterial can also increase from being relatively stiff (i.e., dry-state)to being increasingly stretchable, compressible, and malleable (i.e.,wet-state). The increased compliance accordingly can allow the hydrogelto readily compress under an applied pressure (e.g., during a footstrike on the ground), and in some aspects, to quickly expel at least aportion of its retained water (depending on the extent of compression).While not wishing to be bound by theory, it is believed that thiscompressive compliance alone, water expulsion alone, or both incombination can disrupt the adhesion and/or cohesion of soil at outsole,which prevents or otherwise reduces the accumulation of soil on outsole.

In addition to quickly expelling water, in particular aspects, thecompressed hydrogel is capable of quickly re-absorbing water when thecompression is released (e.g., liftoff from a foot strike during normaluse). As such, during use in a wet or damp environment (e.g., a muddy orwet ground), the hydrogel can dynamically expel and repeatedly take upwater over successive foot strikes, particularly from a wet surface. Assuch, the hydrogel can continue to prevent soil accumulation overextended periods of time (e.g., during an entire competitive match),particularly when there is ground water available for re-uptake.

Water Uptake Capacity—

According to one aspect of the present disclosure, the polymerichydrogel material (e.g., hydrogel present as a sample of a portion of anoutsole component prepared according to the Component SamplingProcedure, the outsole component having the hydrogel present at ordefining a side or surface of the outsole from which the sample wastaken) has a water uptake capacity at 24 hours greater than 40 percentby weight, as characterized by the Water Uptake Capacity Test with theComponent Sampling Procedure, each as described below. In some aspects,it is believed that if a particular outsole is not capable of taking upgreater than 40 percent by weight in water within a 24-hour period,either due to its water uptake rate being too slow, or its ability totake up water is too low (e.g., due to its thinness, not enough hydrogelcan be present, or the overall capacity of the hydrogel to take up wateris too low), then the outsole may not be effective in preventing orreducing soil accumulation.

For the purpose of this disclosure, the term “overall water uptakecapacity” is used to represent the amount of water taken up by thehydrogel as a percentage by weight of dry hydrogel. The procedure formeasuring overall water uptake capacity can include measurement of the“dry” weight of the hydrogel, immersion of the hydrogel in water atambient temperature (about 23 degrees C.) for a predetermined amount oftime, followed by re-measurement of the weight of the hydrogel when“wet”.

For the purpose of this disclosure, the term “weight” refers to a massvalue, such as having the units of grams, kilograms, and the like.Further, the recitations of numerical ranges by endpoints include theendpoints and all numbers within that numerical range. For example, aconcentration ranging from 40 percent by weight to 60 percent by weightincludes concentrations of 40 percent by weight, 60% by weight, and allconcentrations there between (e.g., 40.1 percent, 41 percent, 45percent, 50 percent, 52.5 percent, 55 percent, 59 percent, etc.).

Furthermore, any range in parameters that is stated herein as being“between [a 1^(st) number] and [a 2^(nd) number]” or “between [a 1^(st)number] to [a 2^(nd) number]” is intended to be inclusive of the recitednumbers. In other words, the ranges are meant to be interpretedsimilarly as to a range that is specified as being “from [a 1st number]to [a 2^(nd) number]”.

In further aspects, the hydrogel (including a side or surface of anoutsole component formed of the hydrogel) has a water uptake capacity at24 hours greater than 50 percent by weight, greater than 100 percent byweight, greater than 150 percent by weight, or greater than 200 percentby weight. In other aspects, the hydrogel has a water uptake capacity at24 hours less than 900 percent by weight, less than 750 percent byweight, less than 600 percent by weight or less than 500 percent byweight.

In particular aspects, the hydrogel (including a side or surface of anoutsole formed of the hydrogel) has a water uptake capacity at 24 hoursranging from 40 percent by weight to 900 percent by weight. For example,the hydrogel can have a water uptake capacity ranging from 100 percentby weight to 900 percent by weight, from 100 percent by weight to 750percent by weight, from 100 percent by weight to 700 percent by weight,from 150 percent by weight to 600 percent by weight, from 200 percent byweight to 500 percent by weight, or from 300 percent by weight to 500percent by weight.

These water uptake capacities can be determined by the Water UptakeCapacity Test with the Component Sampling Procedure, and can apply tosamples taken at any suitable representative location along the outsole,where the film component forms the outermost layer of the outsole. Insome cases, samples can be taken from one or more of the forefootregion, the midfoot region, and/or the heel region; from each of theforefoot region, the midfoot region, and the heel region; from withinone or more of the traction element clusters (between the tractionelements) at the forefoot region, the midfoot region, and/or the heelregion; from of the traction element clusters; on planar regions of thetraction elements (for aspects in which the material is present on thetraction elements), and combinations thereof.

As discussed below, the water uptake capacity of the hydrogel (includinga side or surface of an outsole formed of the hydrogel) canalternatively be measured in a simulated environment, such as using thehydrogel co-extruded with a backing substrate (e.g., third polymericmaterial) in a layered film. The backing substrate can be produced fromany suitable thermoset or thermoplastic material that is compatible withthe hydrogel, such as, without limitation, a material that isconventionally used to form an outsole backing plate. As such, suitablewater uptake capacities at 24 hours for the hydrogel as co-extruded orlaminated with a backing substrate, as characterized by the Water UptakeCapacity Test with the Co-extruded or Laminated Film Sampling Procedure,include those discussed above for the Water Uptake Capacity Test withthe Component Sampling Procedure.

Additionally, it has been found that when the hydrogel is secured toanother surface, such as being thermally or adhesively bonded to asubstrate (e.g., the third polymeric material), the interfacial bondformed between the hydrogel and the outsole substrate can restrict theextent that the hydrogel can take up water and/or swell. As such, it isbelieved that the hydrogel as bonded to a substrate or co-extruded witha substrate can potentially have a lower water uptake capacity and/or alower swell capacity compared to the same hydrogel in a neat materialform, including neat film form.

As such, the water uptake capacity and the water uptake rate of theoutsole component can also be characterized based on the hydrogel inneat form (e.g., an isolated film that is not bonded to anothermaterial). The hydrogel in neat form can have a water uptake capacity at24 hours greater than 40 percent by weight, greater than 100 percent byweight, greater than 300 percent by weight, or greater than 1000 percentby weight, as characterized by the Water Uptake Capacity Test with theNeat Film Sampling Procedure or the Neat Material Sampling Procedure.The hydrogel in neat form can also have a water uptake capacity at 24hours less than 900 percent by weight, less than 800 percent by weight,less than 700 percent by weight, less than 600 percent by weight or lessthan 500 percent by weight.

In particular aspects, the hydrogel in neat form has a water uptakecapacity at 24 hours ranging from 40 percent by weight to 900 percent byweight, from 150 percent by weight to 700 percent by weight, from 200percent by weight to 600 percent by weight, or from 300 percent byweight to 500 percent by weight.

Water Uptake Rate—

The outsole component (including a side or surface of an outsole formedof the hydrogel) can have a water uptake rate greater than 20grams/(square meter/square root of minutes) or 20 gms/m²/√min, ascharacterized by the Water Uptake Rate Test with the Component SamplingProcedure. As discussed above, in some aspects, the outsole (e.g., thehydrogel) can take up water between the compressive cycles of footstrikes, which is believed to at least partially replenish the materialbetween the foot strikes.

As such, in further aspects, the outsole component (including a side orsurface of an outsole formed of the hydrogel) has a water uptake rategreater than 20 gms/m²/√min, greater than 100 gms/m²/√min, greater than200 gms/m²/√min, greater than 400 gms/m²/√min, or greater than 600gms/m²/√min. In particular aspects, the outsole has a water uptake rateranging from 1 to 1,500 gms/m²/√min, 20 to 1,300 gms/m²/√min, from 30 to1,200 gms/m²/√min, from 30 to 800 gms/m²/√min, from 100 to 800gms/m²/√min, from 100 to 600 gms/m²/√min, from 150 to 450 gms/m²/√min,from 200 to 1,000 gms/m²/√min, from 400 to 1,000 gms/m²/√min, or from600 to 900 gms/m²/√min.

Suitable water uptake rates for the hydrogel as secured to a co-extrudedbacking substrate (e.g., third polymeric material), as characterized bythe Water Uptake Rate Test with the Co-extruded or Laminated FilmSampling Procedure, and as provided in neat form, as characterized bythe Water Uptake Rate Test with the Neat Film Sampling Procedure, eachinclude those discussed above for the Water Uptake Rate Test with theComponent Sampling Procedure.

Swelling Capacity—

In certain aspects, the outsole component (including a side or surfaceof an outsole formed of the hydrogel) can swell, increasing thehydrogel's thickness and/or volume, due to water uptake. This swellingof the hydrogel can be a convenient indicator showing that the hydrogelis taking up water, and can assist in rendering the hydrogel compliant.In some aspects, the outsole has an increase in material thickness (orswell thickness increase) at 1 hour of greater than 20 percent orgreater than 50 percent, for example ranging from 30 percent to 350percent, from 50 percent to 400 percent, from 50 percent to 300 percent,from 100 percent to 300 percent, from 100 percent to 200 percent, orfrom 150 percent to 250 percent, as characterized by the SwellingCapacity Test with the Component Sampling Procedure. In further aspects,the outsole has an increase in material thickness at 24 hours rangingfrom 45 percent to 400 percent, from 100 percent to 350 percent, or from150 percent to 300 percent.

Additionally, the hydrogel (including a side or surface of an outsoleformed of the hydrogel) can have an increase in material volume (orvolumetric swell increase) at 1 hour of greater than 50 percent, forexample ranging from 10 percent to 130 percent, from 30 percent to 100percent, or from 50 percent to 90 percent. Moreover, the outsole canhave an increase in material volume at 24 hours ranging from 25 percentto 200 percent, from 50 percent to 150 percent, or from 75 percent to100 percent.

For co-extruded or laminated film simulations, suitable increases inmaterial thickness and volume at 1 hour and 24 hours for the hydrogel assecured to a co-extruded or lamination backing substrate, ascharacterized by the Swelling Capacity Test with the Co-extruded orLaminated Film Sampling Procedure, include those discussed above for theSwelling Capacity Test with the Component Sampling Procedure.

The material in neat form can have an increase in material thickness at1 hour ranging from 35 percent to 400 percent, from 50 percent to 300percent, or from 100 percent to 200 percent, as characterized by theSwelling Capacity Test with the Neat Film Sampling Procedure. In somefurther aspects, the material in neat form can have an increase inmaterial thickness at 24 hours ranging 45 percent to 500 percent, from100 percent to 400 percent, or from 150 percent to 300 percent.Correspondingly, the material in neat form can have an increase inmaterial volume at 1 hour ranging from 50 percent to 500 percent, from75 percent to 400 percent, or from 100 percent to 300 percent.

Contact Angle—

In some aspects, the surface of the hydrogel forms a side or surface ofthe outsole, wherein the side or surface has hydrophilic properties. Thehydrophilic properties of the hydrogel's surface can be characterized bydetermining the static sessile drop contact angle of the hydrogel'ssurface. Accordingly, in some aspects, the hydrogel's surface in a drystate has a static sessile drop contact angle (or dry-state contactangle) of less than 105 degrees, or less than 95 degrees, less than 85degrees, as characterized by the Contact Angle Test. The Contact AngleTest can be conducted on a sample obtained in accordance with theComponent Sampling Procedure, the Co-Extruded or Laminated Film SamplingProcedure, or the Neat Film Sampling Procedure. In some further aspects,the hydrogel in a dry state has a static sessile drop contact angleranging from 60 degrees to 100 degrees, from 70 degrees to 100 degrees,or from 65 degrees to 95 degrees.

In other aspects, the hydrogel's surface in a wet state has a staticsessile drop contact angle (or wet-state contact angle) of less than 90degrees, less than 80 degrees, less than 70 degrees, or less than 60degrees. In some further aspects, the surface in a wet state has astatic sessile drop contact angle ranging from 45 degrees to 75 degrees.In some cases, the dry-state static sessile drop contact angle of thesurface is greater than the wet-state static sessile drop contact angleof the surface by at least 10 degrees, at least 15 degrees, or at least20 degrees, for example from 10 degrees to 40 degrees, from 10 degreesto 30 degrees, or from 10 degrees to 20 degrees.

Coefficient of Friction—

The surface of the hydrogel, including the surface of an outsole canalso exhibit a low coefficient of friction when the hydrogel is wet.Examples of suitable coefficients of friction for the hydrogel in a drystate (or dry-state coefficient of friction) are less than 1.5, forinstance ranging from 0.3 to 1.3 or from 0.3 to 0.7, as characterized bythe Coefficient of Friction Test. The Coefficient of Friction Test canbe conducted on a sample obtained in accordance with the ComponentSampling Procedure, the Co-Extruded or Laminated Film SamplingProcedure, or the Neat Film Sampling Procedure. Examples of suitablecoefficients of friction for the hydrogel in a wet state (or wet-statecoefficient of friction) are less than 0.8 or less than 0.6, forinstance ranging from 0.05 to 0.6, from 0.1 to 0.6, or from 0.3 to 0.5.Furthermore, the hydrogel can exhibit a reduction in its coefficient offriction from its dry state to its wet state, such as a reductionranging from 15 percent to 90 percent, or from 50 percent to 80 percent.In some cases, the dry-state coefficient of friction is greater than thewet-state coefficient of friction for the hydrogel, for example beinghigher by a value of at least 0.3 or 0.5, such as 0.3 to 1.2 or 0.5 to1.

Storage Modulus—

The compliance of the hydrogel, including an external or ground-facinglayer of an outsole comprising the hydrogel, can be characterized bybased on the hydrogel's storage modulus in the dry state (whenequilibrated at 0 percent relative humidity (RH)), and in a partiallywet state (e.g., when equilibrated at 50 percent RH or at 90 percentRH), and by reductions in its storage modulus between the dry and wetstates. In particular, the hydrogel can have a reduction in storagemodulus (ΔE′) from the dry state relative to the wet state. A reductionin storage modulus as the water concentration in the hydrogel increasescorresponds to an increase in compliance, because less stress isrequired for a given strain/deformation.

In some aspects, the hydrogel exhibits a reduction in the storagemodulus from its dry state to its wet state (50 percent RH) of more than20 percent, more than 40 percent, more than 60 percent, more than 75percent, more than 90 percent, or more than 99 percent, relative to thestorage modulus in the dry state, and as characterized by the StorageModulus Test with the Neat Film Sampling Process. In some furtheraspects, the dry-state storage modulus of the hydrogel is greater thanits wet-state (50 percent RH) storage modulus by more than 25megaPascals (MPa), by more than 50 MPa, by more than 100 MPa, by morethan 300 MPa, or by more than 500 MPa, for example ranging from 25 MPato 800 MPa, from 50 MPa to 800 MPa, from 100 MPa to 800 MPa, from 200MPa to 800 MPa, from 400 MPa to 800 MPa, from 25 MPa to 200 MPa, from 25MPa to 100 MPa, or from 50 MPa to 200 MPa. Additionally, the dry-statestorage modulus can range from 40 MPa to 800 MPa, from 100 MPa to 600MPa, or from 200 MPa to 400 MPa, as characterized by the Storage ModulusTest. Additionally, the wet-state storage modulus can range from 0.003MPa to 100 MPa, from 1 MPa to 60 MPa, or from 20 MPa to 40 MPa.

In other aspects, the hydrogel exhibits a reduction in the storagemodulus from its dry state to its wet state (90 percent RH) of more than20 percent, more than 40 percent, more than 60 percent, more than 75percent, more than 90 percent, or more than 99 percent, relative to thestorage modulus in the dry state, and as characterized by the StorageModulus Test with the Neat Film Sampling Process. In further aspects,the dry-state storage modulus of the hydrogel is greater than itswet-state (90 percent RH) storage modulus by more than 25 megaPascals(MPa), by more than 50 MPa, by more than 100 MPa, by more than 300 MPa,or by more than 500 MPa, for example ranging from 25 MPa to 800 MPa,from 50 MPa to 800 MPa, from 100 MPa to 800 MPa, from 200 MPa to 800MPa, from 400 MPa to 800 MPa, from 25 MPa to 200 MPa, from 25 MPa to 100MPa, or from 50 MPa to 200 MPa. Additionally, the dry-state storagemodulus can range from 40 MPa to 800 MPa, from 100 MPa to 600 MPa, orfrom 200 MPa to 400 MPa, as characterized by the Storage Modulus Test.Additionally, the wet-state storage modulus can range from 0.003 MPa to100 MPa, from 1 MPa to 60 MPa, or from 20 MPa to 40 MPa.

In addition to a reduction in storage modulus, the hydrogel can alsoexhibit a reduction in its glass transition temperature from the drystate (when equilibrated at 0 percent relative humidity (RH) to the wetstate (when equilibrated at 90% RH). While not wishing to be bound bytheory, it is believed that the water taken up by the hydrogelplasticizes the hydrogel, which reduces its storage modulus and itsglass transition temperature, rendering the material more compliant(e.g., compressible, expandable, and stretchable).

Glass Transition Temperature—

In some aspects, the hydrogel can exhibit a reduction in glasstransition temperature (ΔT_(g)) from its dry-state (0 percent RH) glasstransition temperature to its wet-state glass transition (90% RH)temperature of more than a 5 degree C. difference, more than a 6 degreeC. difference, more than a 10 degree C. difference, or more than a 15degree C. difference, as characterized by the Glass TransitionTemperature Test with the Neat Film Sampling Process or the NeatMaterial Sampling Process. For instance, the reduction in glasstransition temperature (ΔT_(g)) can range from more than a 5 degree C.difference to a 40 degree C. difference, from more than a 6 degree C.difference to a 50 degree C. difference, form more than a 10 degree C.difference to a 30 degree C. difference, from more than a 30 degree C.difference to a 45 degree C. difference, or from a 15 degree C.difference to a 20 degree C. difference. The hydrogel can also exhibit adry glass transition temperature ranging from −40 degrees C. to −80degrees C. or from −40 degrees C. to −60 degrees C.

Alternatively (or additionally), the reduction in glass transitiontemperature (ΔT_(g)) can range from a 5 degree C. difference to a 40degree C. difference, form a 10 degree C. difference to a 30 degree C.difference, or from a 15 degree C. difference to a 20 degree C.difference. The material can also exhibit a dry glass transitiontemperature ranging from −40 degrees C. to −80 degrees C. or from −40degrees C. to −60 degrees C.

In various aspects, the polymeric hydrogel material is a thermoplastichydrogel having a melting point of less than 150 degrees C. For example,the onset of melting of the polymeric hydrogel material can occurbetween 90 degrees C. and 150 degrees C., including between 90 degreesC. and 135 degrees C., and between 110 degrees C. and 135 degrees C.Alternatively, the polymeric hydrogel material is a thermoplastichydrogel having a melting point of greater than 150 degrees C. Forexample, the onset of melting of the polymeric hydrogel material canoccur between 150 degrees C. and 190 degrees C., including between 150degrees C. and 180 degrees C.

In addition to being effective at preventing soil accumulation, theoutsole comprising the ground-facing layer of hydrogel has also beenfound to be sufficiently durable for its intended use on the externallyfacing side or surface of the article. Durability is based, at least inpart, on the nature and strength of the interfacial bond of the outsoleto an upper that comprises part of the finished article of footwear, aswell as the physical properties of the hydrogel in the outsole itself.For example, during the useful life of the finished article of footwear,it is desirable that the outsole may not delaminate from the upper, andit can be substantially abrasion resistant or wear resistant (e.g.,maintaining its structural integrity without rupturing or tearing). Invarious aspects, the useful life of the outsole (and the article offootwear containing it) is at least 10 hours, 20 hours, 50 hours, 100hours, 120 hours, or 150 hours of use. For example, in someapplications, the useful life of the outsole ranges from 20 hours to 120hours. In other applications, the useful life of the outsole ranges from50 hours to 100 hours of use.

The phrase “externally-facing” as used in reference to an element ormaterial or layer refers to a surface or side of the element that isdirected toward or facing the exterior of the article when the elementis present in an article during its intended use. If the article isfootwear, an externally-facing element can be “ground-facing” in otherwords, a surface or side of the element is directed toward or facing theground when the element is present in an article of footwear duringnormal use, i.e., the element is positioned toward the ground duringnormal use by a wearer when in a standing position, and thus can contactthe ground including unpaved surfaces when the footwear is used in aconventional manner, such as standing, walking or running on an unpavedsurface. In other words, even though the element may not necessarily befacing the ground during various steps of manufacturing or shipping, ifthe element is intended to face the ground during normal use by awearer, the element is understood to be ground-facing.

In some circumstances, due to the presence of elements such as tractionelements, the ground-facing surface can be positioned toward the groundduring conventional use but may not necessarily come into contact theground. For example, on hard ground or paved surfaces, the terminal endsof traction elements on the outsole can directly contact the ground,while portions of the outsole located between the traction elements donot. As described in this example, the portions of the outsole locatedbetween the traction elements are considered to be ground-facing eventhough they may not directly contact the ground in all circumstances.

The hydrogel material in the outsole component can comprise a polymerichydrogel. The hydrogel material can be any material that takes up water,to provide an outsole component that can take up a desired amount ofwater. The hydrogel material can comprise, consist of, or consistessentially of polymers or copolymers of polyurethane, polyurea,polyester, polycarbonate, polyetheramide, addition polymers ofethylenically unsaturated monomers, or any combination thereof.

As used herein, the term “polymer” refers to a molecule havingpolymerized units of one or more species of monomer. One skilled in theart will understand that the term “polymer” includes both homopolymers(i.e., a polymer in which the monomer species are the same) andcopolymers. The term “copolymer” refers to a polymer having polymerizedunits of two or more species of monomers, and is understood to includeterpolymers (i.e., copolymers having three monomer species). In afurther aspect, the “monomer” can include different functional groups orsegments, but for simplicity is generally referred to as a monomer. Asused herein, reference to “a” polymer or other chemical compound refersto one or more molecules of the polymer or chemical compound, ratherthan being limited to a single molecule of the polymer or chemicalcompound. Furthermore, the one or more molecules may or may not beidentical, so long as they fall under the category of the chemicalcompound. Thus, for example, “a” polylaurolactam is interpreted toinclude one or more polymer molecules of the polylaurolactam, where thepolymer molecules may or may not be identical (e.g., different molecularweights and/or isomers).

For the purpose of this disclosure, the terms “at least one” and “one ormore of” an element are used interchangeably and may have the samemeaning. These terms, which refer to the inclusion of a single elementor a plurality of the elements, may also be represented by the suffix“(s)” at the end of the element. For example, “at least onepolyurethane”, “one or more polyurethanes”, and “polyurethane(s)” may beused interchangeably and are intended to have the same meaning.

Unless otherwise indicated, any of the functional groups or chemicalcompounds described herein can be substituted or unsubstituted. A“substituted” group or chemical compound, such as an alkyl, alkenyl,alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxyl, ester,ether, or carboxylic ester refers to an alkyl, alkenyl, alkynyl,cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxyl, ester, ether, orcarboxylic ester group, has at least one hydrogen radical that issubstituted with a non-hydrogen radical (i.e., a substituent). Examplesof non-hydrogen radicals (or substituents) include, but are not limitedto, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, ether, aryl,heteroaryl, heterocycloalkyl, hydroxyl, oxy (or oxo), alkoxyl, ester,thioester, acyl, carboxyl, cyano, nitro, amino, amido, sulfur, and halo.When a substituted alkyl group includes more than one non-hydrogenradical, the substituents can be bound to the same carbon or two or moredifferent carbon atoms.

In an aspect, the polymeric hydrogel can comprise, consist of or consistessentially of a polyurethane hydrogel. Polyurethane hydrogels areprepared from one or more diisocyanate and one or more hydrophilic diol.The polymer can also include a hydrophobic diol in addition to thehydrophilic diol. The polymerization is normally carried out usingroughly an equivalent amount of the diol and diisocyanate. Examples ofhydrophilic diols are polyethylene glycols or copolymers of ethyleneglycol and propylene glycol. The diisocyanate can be selected from awide variety of aliphatic or aromatic diisocyanates. The hydrophobicityof the resulting polymer is determined by the amount and type of thehydrophilic diols, the type and amount of the hydrophobic diols, and thetype and amount of the diisocyanates. Examples of commercially-availablethermoplastic polyurethane hydrogels include, but are not limited tothose under the tradename “TECOPHILIC”, such as TG-500, TG-2000,SP-80A-150, SP-93A-100, SP-60D-60 (Lubrizol, Countryside, Ill.),“ESTANE” (e.g., ALR G 500; Lubrizol, Countryside, Ill.). Additionaldetails regarding polyurethane are provided herein.

In various aspects, the polyurethane hydrogel is a thermoplasticpolyurethane hydrogel having a melting point of less than 150 degreesC., including between 90 degrees C. and 135 degrees C., and between 110degrees C. and 135 degrees C. Alternatively, the polyurethane hydrogelis a thermoplastic polyurethane hydrogel having a melting point ofgreater than 150 degrees C., including between 150 degrees C. and 190degrees C., and between 150 degrees C. and 180 degrees C.

In an aspect, the polymeric hydrogel can comprise, consist of or consistessentially of a polyurea hydrogel. Polyurea hydrogels are prepared fromone or more diisocyanate and one or more hydrophilic diamine. Thepolymer can also include a hydrophobic diamine in addition to thehydrophilic diamines. The polymerization is normally carried out usingroughly an equivalent amount of the diamine and diisocyanate. Typicalhydrophilic diamines are amine-terminated polyethylene oxides andamine-terminated copolymers of polyethylene oxide/polypropylene.Examples are “JEFFAMINE” diamines sold by Huntsman (The Woodlands, Tex.,USA). The diisocyanate can be selected from a wide variety of aliphaticor aromatic diisocyanates. The hydrophobicity of the resulting polymeris determined by the amount and type of the hydrophilic diamine, thetype and amount of the hydrophobic amine, and the type and amount of thediisocyanate. Additional details regarding polyurea are provided herein.

In an aspect, the polymeric hydrogel can comprise, consist of, orconsist essentially of a polyester hydrogel. Polyester hydrogels can beprepared from dicarboxylic acids (or dicarboxylic acid derivatives) anddiols where part or all of the diol is a hydrophilic diol. Examples ofhydrophilic diols are polyethylene glycols or copolymers of ethyleneglycol and propylene glycol. A second hydrophobic diol can also be usedto control the polarity of the final polymer. One or more diacid can beused which can be either aromatic or aliphatic. Of particular interestare block polyesters prepared from hydrophilic diols and lactones ofhydroxyacids. The lactone is polymerized on the each end of thehydrophilic diol to produce a triblock polymer. In addition, thesetriblock segments can be linked together to produce a multiblock polymerby reaction with a dicarboxylic acid. Additional details regardingpolyurea are provided herein.

In an aspect, the polymeric hydrogel can comprise, consist of, or orconsist essentially of a polycarbonate hydrogel. Polycarbonates aretypically prepared by reacting a diol with phosgene or a carbonatediester. A hydrophilic polycarbonate is produced when part or all of thediol is a hydrophilic diol. Examples of hydrophilic diols are hydroxylterminated polyethers of ethylene glycol or polyethers of ethyleneglycol with propylene glycol. A second hydrophobic diol can also beincluded to control the polarity of the final polymer. Additionaldetails regarding polycarbonate are provided herein.

In an aspect, the polymeric hydrogel can comprise, consist of, orconsist essentially of a polyetheramide hydrogel. Polyetheram ides areprepared from dicarboxylic acids (or dicarboxylic acid derivatives) andpolyether diamines (a polyether terminated on each end with an aminogroup). Hydrophilic amine-terminated polyethers produce hydrophilicpolymers that will swell with water. Hydrophobic diamines can be used inconjunction with hydrophilic diamines to control the hydrophilicity ofthe final polymer. In addition, the type dicarboxylic acid segment canbe selected to control the polarity of the polymer and the physicalproperties of the polymer. Typical hydrophilic diamines areamine-terminated polyethylene oxides and amine-terminated copolymers ofpolyethylene oxide/polypropylene. Examples are “JEFFAMINE” diamines soldby Huntsman (The Woodlands, Tex., USA). Additional details regardingpolyetheramide are provided herein.

In an aspect, the polymeric hydrogel can comprise, consist of, orconsist essentially of a hydrogel formed of addition polymers ofethylenically unsaturated monomers. The addition polymers ofethylenically unsaturated monomers can be random polymers. Polymersprepared by free radical polymerization of one of more hydrophilicethylenically unsaturated monomer and one or more hydrophobicethylenically unsaturated monomers. Examples of hydrophilic monomers areacrylic acid, methacrylic acid, 2-acrylamido-2-methylpropane sulphonicacid, vinyl sulphonic acid, sodium p-styrene sulfonate,[3-(methacryloylamino)propyl]trimethylammonium chloride, 2-hydroxyethylmethacrylate, acrylamide, N, N-dimethylacrylamide, 2-vinylpyrrolidone,(meth)acrylate esters of polyethylene glycol, and (meth)acrylate estersof polyethylene glycol monomethyl ether. Examples of hydrophobicmonomers are (meth)acrylate esters of C₁ to C₄ alcohols, polystyrene,polystyrene methacrylate macromonomer and mono(meth)acrylate esters ofsiloxanes. The water uptake and physical characteristics can be tuned byselection of the monomer and the amounts of each monomer type.Additional details regarding ethylenically unsaturated monomers areprovided herein.

The addition polymers of ethylenically unsaturated monomers can be combpolymers. Comb polymers are produced when one of the monomers is amacromer (an oligomer with an ethylenically unsaturated group one end).In one case the main chain is hydrophilic while the side chains arehydrophobic. Alternatively the comb backbone can be hydrophobic whilethe side chains are hydrophilic. An example is a backbone of ahydrophobic monomer such as styrene with the methacrylate monoester ofpolyethylene glycol.

The addition polymers of ethylenically unsaturated monomers can be blockpolymers. Block polymers of ethylenically unsaturated monomers can beprepared by methods such as anionic polymerization or controlled freeradical polymerization. Hydrogels are produced when the polymer has bothhydrophilic blocks and hydrophobic blocks. The polymer can be a diblockpolymer (A-B) polymer, triblock polymer (A-B-A) or multiblock polymer.Triblock polymers with hydrophobic end blocks and a hydrophilic centerblock are most useful for this application. Block polymers can beprepared by other means as well. Partial hydrolysis of polyacrylonitrilepolymers produces multiblock polymers with hydrophilic domains(hydrolyzed) separated by hydrophobic domains (unhydrolyzed) such thatthe partially hydrolyzed polymer acts as a hydrogel. The hydrolysisconverts acrylonitrile units to hydrophilic acrylamide or acrylic acidunits in a multiblock pattern.

The polymeric hydrogel can comprise, consist of, or consist essentiallyof a hydrogel formed of copolymers. In some aspects, the polymerichydrogel can comprise a polyurethane/polyurea copolymer,polyurethane/polyester copolymer, or a polyester/polycarbonatecopolymer.

The hydrogel material can comprise a polymer network. In other words,the hydrogel can include any suitable polymer chains that provide thedesired functional properties (e.g., water uptake, swelling, and moregenerally, preventing soil accumulation) and desirably provide gooddurability for the article. For example, the hydrogel can be based onone or more polyurethanes, one or more polyureas, one or morepolyesters, one or more polyetheramide, one or ore polymers ofethylenically unsaturated monomers, one or more polyamides, one or morepolyolefins, and combinations thereof (e.g., a hydrogel based onpolyurethane(s) and polyamide(s)). The hydrogel or cross-linkedpolymeric network can include a plurality of copolymer chains wherein atleast a portion of the copolymer chains each include a polyurethanesegment, a polyamide segment, or a combination thereof. In some aspects,the one or more polyurethanes, one or more polyamides, one or morepolyolefins, and combinations thereof include polysiloxane segmentsand/or ionomer segments.

In some aspects, the hydrogel material compositionally comprises ahydrophilic polymer and optionally one or more additives. In furtheraspects, the hydrogel compositionally comprises a polymeric network(e.g., a hydrophilic polymeric network) and optionally one or moreadditives. In some aspects, the polymeric network is preferably aplurality of cross-linked (or cross-linkable) polymer chains, where thepolymer chains can be homopolymers, copolymers, or a combination of bothhomopolymers and copolymers. When cross-linked, the network can beeither physically or covalently or both physically and covalentlycross-linked.

For a physical cross-link, a copolymer chain can form entangled regionsand/or crystalline regions through non-covalent bonding interactions,such as, for example, an ionic bond, a polar bond, and/or a hydrogenbond. In particular aspects, the crystalline regions create the physicalcross-link between the copolymer chains. The crystalline regions caninclude hard segments, as described below.

In some aspects, the polymeric network can exhibit sol-gelreversibility, allowing it to function as a thermoplastic polymer, whichcan be advantageous for manufacturing and recyclability. As such, insome aspects, the polymeric network of the hydrogel includes aphysically cross-linked polymeric network to function as a thermoplasticmaterial.

The hydrogels can be characterized as including both hard segments andsoft segments. These hard and soft regions can exist as phase separatedregions within the polymeric network while the hydrogel is in a solid(non-molten) state. The hard segments can form portions of the polymerchain backbones, and can exhibit high polarities, allowing the hardsegments of multiple polymer chains to aggregate together, or interactwith each other, to form semi-crystalline regions in the polymericnetwork. The plurality of polymer chains can comprise one or more hardsegments; and one or more soft segments covalently bonded to the hardsegments, wherein the one or more soft segments are present in thecopolymer chains at a ratio ranging from 20:1 to 110:1 by weightrelative to the one or more hard segments.

A “semi-crystalline” or “crystalline” region has an ordered molecularstructure with sharp melting points, which remains solid until a givenquantity of heat is absorbed and then rapidly changes into a lowviscosity liquid. A “pseudo-crystalline” region has properties of acrystal, but does not exhibit a true crystalline diffraction pattern.For ease of reference, the term “crystalline region” is used herein tocollectively refer to a crystalline region, a semi-crystalline region,and a pseudo-crystalline region of a polymeric network.

In comparison, the soft segments can be longer, more flexible,hydrophilic regions of the polymeric network that allow the polymernetwork to expand and swell under the pressure of taken up water. Thesoft segments can constitute amorphous hydrophilic regions of thehydrogel or cross-linked polymeric network. The soft segments, oramorphous regions, can also form portions of the backbones of thepolymer chains along with the hard segments. Additionally, one or moreportions of the soft segments, or amorphous regions, can be grafted orotherwise represent pendant chains that extend from the backbones at thesoft segments. The soft segments, or amorphous regions, can becovalently bonded to the hard segments, or crystalline regions (e.g.,through carbamate linkages). For example, a plurality of amorphoushydrophilic regions can be covalently bonded to the crystalline regionsof the hard segments.

As used herein, the term “hydrophilic,” refers to polymers having astrong tendency to bind or absorb water, which results in swelling andformation of reversible swelling gels. A “swelling gel” is a gel thatabsorbs an amount of water greater than at least 100 weight percent ofits own weight when immersed in water.

The hydrophilic soft segments of the copolymer chains can comprisepolyether segments, polyester segments, polycarbonate segments, orcombinations thereof. At least a portion of the one or more hydrophilicsoft segments can constitute backbone segments of the copolymer chain.At least a portion of the hydrophilic soft segments can comprise one ormore pendant polyether groups. The one or more hydrophilic soft segmentscan be present in the copolymer chains at a ratio ranging from 40:1 to110:1 by weight relative to the one or more hard segments. The polymericnetwork can be a cross-linked polymeric network. The polymeric networkcan be a network formed of copolymer chains. The polymer chains of thepolymeric network comprise polyurethane chain segments, polyamide chainsegments, or both.

According to another aspect of the present disclosure, the cross-linkedpolymeric network of the hydrogel in the external or ground-facing layerof the outsole includes a plurality of copolymer chains. At least aportion of these copolymer chains comprise a hard segment physicallycross-linked to other hard segments of the copolymer chains and a softsegment covalently bonded to the hard segment, such as through acarbamate group or an ester group.

The hydrogel or cross-linked polymeric network can include a pluralityof copolymer chains. At least a portion of the copolymer chains includea first segment that forms at least a crystalline region with other hardsegments of the copolymer chains and a second segment, such as a softsegment (e.g., a segment having polyether chains or one or more ethergroups) covalently bonded to the first segment. The soft segment formsamorphous regions of the hydrogel or cross-linked polymeric network. Insome cases, the hydrogel or cross-linked polymeric network includes aplurality of copolymer chains, where at least a portion of the copolymerchains has hydrophilic segments.

When the polymeric network of the hydrogel is cross-linked, it has beenfound that the cross-linking density of the cross-linked polymericnetwork can affect the structural integrity and water uptake capacitiesof the hydrogel. For example, if the cross-linking density is too high,the resulting hydrogel can be stiff and less compliant, having arelatively low water uptake and swelling capacity. On the other hand, ifthe cross-linking density is too low, then the resulting hydrogel canlose its structural integrity when saturated. As such, the polymericnetwork(s) of the hydrogel preferably have a cross-linking density thatis selected such that the hydrogel has a desired balance of properties,e.g., it retains its structural integrity, yet is also sufficientlycompliant when partially or fully saturated with water.

The hydrogel material in the layered film of the outsole can be formedvia co-extrusion or lamination with a backing plate or layer comprisinga third polymeric material. Subsequently, a second polymeric material isused to complete the formation of the outsole in a molding process. Thesecond (2^(nd)) polymeric material and/or third (3^(rd)) polymericmaterial can independently be selected to comprise a thermoset polymeror a thermoplastic polymer. The composition of the second and thirdpolymeric materials can be selected to be substantially the samematerial or, alternatively, different materials. When desirable, thesecond and/or third polymeric materials can comprise one or more naturalor synthetic rubbers. The natural or synthetic rubbers can include, butnot be limited to, butadiene rubber, isoprene rubber, or nitrile rubber.The natural or synthetic rubbers can be individually selected as virginmaterials, regrind materials, or a mixture thereof.

Now having described aspects of the hydrogel material in general,additional details are provided regarding the thermoplastic polymersreferenced herein, including thermoplastic hydrogels. In variousaspects, the thermoplastic polymer can include one or more polymersselected from the group consisting of polyesters, polyethers,polyamides, polyurethanes and polyolefins as well as copolymers of eachor combinations thereof, such as those described herein.

In aspects, the thermoplastic polymer can include polymers of the sameor different types of monomers (e.g., homopolymers and copolymers,including terpolymers). In certain aspects, the thermoplastic polymercan include different monomers randomly distributed in the polymer(e.g., a random co-polymer).

For example, the thermoplastic polymer can be a polymer having repeatingpolymeric units of the same chemical structure (segments) which arerelatively harder (hard segments), and repeating polymeric segmentswhich are relatively softer (soft segments). In various aspects, thepolymer has repeating hard segments and soft segments, physicalcrosslinks can be present within the segments or between the segments orboth within and between the segments. Particular examples of hardsegments include isocyanate segments. Particular examples of softsegments include an alkoxy group such as polyether segments andpolyester segments. As used herein, the polymeric segment can bereferred to as being a particular type of polymeric segment such as, forexample, an isocyanate segment (e.g., diisocyanate segment), an alkokypolyamide segment (e.g., a polyether segment, a polyester segment), andthe like. It is understood that the chemical structure of the segment isderived from the described chemical structure. For example, anisocyanate segment is a polymerized unit including an isocyanatefunctional group. When referring to polymeric segments of a particularchemical structure, the polymer can contain up to 10 mol % of segmentsof other chemical structures. For example, as used herein, a polyethersegment is understood to include up to 10 mol % of non-polyethersegments.

In various aspects, the thermoplastic polymer of the outsole component,including but not limited to the thermoplastic hydrogel of the outsolecomponent, has a melting temperature (T_(m)) from about 90 degrees C. toabout 190 degrees C. when determined in accordance with ASTM D3418-97 asdescribed herein below. In a further aspect, the thermoplastic polymerhas a melting temperature (T_(m)) from about 93 degrees C. to about 99degrees C. when determined in accordance with ASTM D3418-97 as describedherein below. In a still further aspect, the thermoplastic polymer has amelting temperature (T_(m)) from about 112 degrees C. to about 118degrees C. when determined in accordance with ASTM D3418-97 as describedherein below.

In various aspects, the thermoplastic polymer has a glass transitiontemperature (T_(g)) from about −20 degrees C. to about 30 degrees C.when determined in accordance with ASTM D3418-97 as described hereinbelow. In a further aspect, the thermoplastic polymer has a glasstransition temperature (T_(g)) from about −13 degree C. to about −7degrees C. when determined in accordance with ASTM D3418-97 as describedherein below. In a still further aspect, the thermoplastic polymer orthermoplastic hydrogel has a glass transition temperature (T_(g)) fromabout 17 degrees C. to about 23 degrees C. when determined in accordancewith ASTM D3418-97 as described herein below.

In various aspects, the thermoplastic polymer has a melt flow index fromabout 10 to about 30 cubic centimeters per 10 minutes (cm³/10 min) whentested in accordance with ASTM D1238-13 as described herein below at 160degrees C. using a weight of 2.16 kilograms (kg). In a further aspect,the thermoplastic polymer has a melt flow index from about 22 cm³/10 minto about 28 cm³/10 min when tested in accordance with ASTM D1238-13 asdescribed herein below at 160 degrees C. using a weight of 2.16 kg.

In various aspects, the thermoplastic polymer has a cold Ross flex testresult of about 120,000 to about 180,000 cycles without cracking orwhitening when tested on a thermoformed plaque of the thermoplasticpolymer in accordance with the cold Ross flex test as described hereinbelow. In a further aspect, the thermoplastic polymer has a cold Rossflex test result of about 140,000 to about 160,000 cycles withoutcracking or whitening when tested on a thermoformed plaque of thethermoplastic polymer in accordance with the cold Ross flex test asdescribed herein below.

In various aspects, the thermoplastic polymer has a modulus from about 5megaPascals (MPa) to about 100 MPa when determined on a thermoformedplaque in accordance with ASTM D412-98 Standard Test Methods forVulcanized Rubber and Thermoplastic Rubbers and ThermoplasticElastomers-Tension with modifications described herein below. In afurther aspect, the thermoplastic polymer has a modulus from about 20MPa to about 80 MPa when determined on a thermoformed plaque inaccordance with ASTM D412-98 Standard Test Methods for Vulcanized Rubberand Thermoplastic Rubbers and Thermoplastic Elastomers-Tension withmodifications described herein below.

In certain aspects, the thermoplastic polymer can be a thermoplasticpolyurethane (also referred to as “TPU”). In aspects, the thermoplasticpolyurethane can be a thermoplastic polyurethane polymer. In suchaspects, the thermoplastic polyurethane polymer can include hard andsoft segments. In aspects, the hard segments can comprise or consist ofisocyanate segments (e.g., diisocyanate segments). In the same oralternative aspects, the soft segments can comprise or consist of alkoxysegments (e.g., polyether segments, or polyester segments, or acombination of polyether segments and polyester segments). In aparticular aspect, the thermoplastic material can comprise or consistessentially of an elastomeric thermoplastic polyurethane havingrepeating hard segments and repeating soft segments.

Thermoplastic Polyurethanes

In aspects, one or more of the thermoplastic polyurethanes can beproduced by polymerizing one or more isocyanates with one or morepolyols to produce polymer chains having carbamate linkages (—N(CO)O—)as illustrated below in Formula 1, where the isocyanate(s) eachpreferably include two or more isocyanate (—NCO) groups per molecule,such as 2, 3, or 4 isocyanate groups per molecule (although,single-functional isocyanates can also be optionally included, e.g., aschain terminating units).

In these aspects, each R₁ and R₂ independently is an aliphatic oraromatic segment. Optionally, each R₂ can be a hydrophilic segment.

Additionally, the isocyanates can also be chain extended with one ormore chain extenders to bridge two or more isocyanates. This can producepolyurethane polymer chains as illustrated below in Formula 2, where R₃includes the chain extender. As with each R₁ and R₃, each R₃independently is an aliphatic or aromatic segment.

Each segment R₁, or the first segment, in Formulas 1 and 2 canindependently include a linear or branched C₃₋₃₀ segment, based on theparticular isocyanate(s) used, and can be aliphatic, aromatic, orinclude a combination of aliphatic portions(s) and aromatic portion(s).The term “aliphatic” refers to a saturated or unsaturated organicmolecule that does not include a cyclically conjugated ring systemhaving delocalized pi electrons. In comparison, the term “aromatic”refers to a cyclically conjugated ring system having delocalized pielectrons, which exhibits greater stability than a hypothetical ringsystem having localized pi electrons.

Each segment R₁ can be present in an amount of 5% to 85% by weight, from5% to 70% by weight, or from 10% to 50% by weight, based on the totalweight of the reactant monomers.

In aliphatic embodiments (from aliphatic isocyanate(s)), each segment R₁can include a linear aliphatic group, a branched aliphatic group, acycloaliphatic group, or combinations thereof. For instance, eachsegment R₁ can include a linear or branched C₃₋₂₀ alkylene segment(e.g., C₄₋₁₅ alkylene or C₆₋₁₀ alkylene), one or more C₃₋₈ cycloalkylenesegments (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, or cyclooctyl), and combinations thereof.

Examples of suitable aliphatic diisocyanates for producing thepolyurethane polymer chains include hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), butylenediisocyanate (BDI),bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylenediisocyanate (TMDI), bisisocyanatomethylcyclohexane,bisisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI),cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate(H12MDI), diisocyanatododecane, lysine diisocyanate, and combinationsthereof.

In an aspect, the diisocyanate segments can include aliphaticdiisocyanate segments. In one aspect, a majority of the diisocyanatesegments comprise the aliphatic diisocyanate segments. In an aspect, atleast 90% of the diisocyanate segments are aliphatic diisocyanatesegments. In an aspect, the diisocyanate segments consist essentially ofaliphatic diisocyanate segments. In an aspect, the aliphaticdiisocyanate segments are substantially (e.g., about 50% or more, about60% or more, about 70% or more, about 80% or more, about 90% or more)linear aliphatic diisocyanate segments. In an aspect, at least 80% ofthe aliphatic diisocyanate segments are aliphatic diisocyanate segmentsthat are free of side chains. In an aspect, the aliphatic diisocyanatesegments include C2-C10 linear aliphatic diisocyanate segments.

In aromatic embodiments (from aromatic isocyanate(s)), each segment R₁can include one or more aromatic groups, such as phenyl, naphthyl,tetrahydronaphthyl, phenanthrenyl, biphenylenyl, indanyl, indenyl,anthracenyl, and fluorenyl. Unless otherwise indicated, an aromaticgroup can be an unsubstituted aromatic group or a substituted aromaticgroup, and can also include heteroaromatic groups. “Heteroaromatic”refers to monocyclic or polycyclic (e.g., fused bicyclic and fusedtricyclic) aromatic ring systems, where one to four ring atoms areselected from oxygen, nitrogen, or sulfur, and the remaining ring atomsare carbon, and where the ring system is joined to the remainder of themolecule by any of the ring atoms. Examples of suitable heteroarylgroups include pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl,imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl,oxadiazolyl, furanyl, quinolinyl, isoquinolinyl, benzoxazolyl,benzimidazolyl, and benzothiazolyl.

Examples of suitable aromatic diisocyanates for producing thepolyurethane polymer chains include toluene diisocyanate (TDI), TDIadducts with trimethyloylpropane (TMP), methylene diphenyl diisocyanate(MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate(TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate,para-phenylene diisocyanate (PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4′-dibenzyl diisocyanate (DBDI),4-chloro-1,3-phenylene diisocyanate, and combinations thereof. In someaspects, the polymer chains are substantially free of aromatic groups.

In particular aspects, the polyurethane polymer chains are produced fromdiisocynates including HMDI, TDI, MDI, H₁₂ aliphatics, and combinationsthereof. For example, the low processing temperature polymericcomposition of the present disclosure can comprise one or morepolyurethane polymer chains are produced from diisocyanates includingHMDI, TDI, MDI, H12 aliphatics, and combinations thereof.

In certain aspects, polyurethane chains which are crosslinked (e.g.,partially crosslinked polyurethane polymers which retain thermoplasticproperties) or which can be crosslinked, can be used in accordance withthe present disclosure. It is possible to produce crosslinked orcrosslinkable polyurethane polymer chains using multi-functionalisocyantes. Examples of suitable triisocyanates for producing thepolyurethane polymer chains include TDI, HDI, and IPDI adducts withtrimethyloylpropane (TMP), uretdiones (i.e., dimerized isocyanates),polymeric MDI, and combinations thereof.

Segment R₃ in Formula 2 can include a linear or branched C₂-C₁₀ segment,based on the particular chain extender polyol used, and can be, forexample, aliphatic, aromatic, or polyether. Examples of suitable chainextender polyols for producing the polyurethane polymer chains includeethylene glycol, lower oligomers of ethylene glycol (e.g., diethyleneglycol, triethylene glycol, and tetraethylene glycol), 1,2-propyleneglycol, 1,3-propylene glycol, lower oligomers of propylene glycol (e.g.,dipropylene glycol, tripropylene glycol, and tetrapropylene glycol),1,4-butylene glycol, 2,3-butylene glycol, 1,6-hexanediol,1,8-octanediol, neopentyl glycol, 1,4-cyclohexanedimethanol,2-ethyl-1,6-hexanediol, 1-methyl-1,3-propanediol,2-methyl-1,3-propanediol, dihydroxyalkylated aromatic compounds (e.g.,bis(2-hydroxyethyl) ethers of hydroquinone and resorcinol,xylene-a,a-diols, bis(2-hydroxyethyl) ethers of xylene-a,a-diols, andcombinations thereof.

Segment R₂ in Formula 1 and 2 can include a polyether group, a polyestergroup, a polycarbonate group, an aliphatic group, or an aromatic group.Each segment R₂ can be present in an amount of 5% to 85% by weight, from5% to 70% by weight, or from 10% to 50% by weight, based on the totalweight of the reactant monomers.

In some examples, at least one R₂ segment of the thermoplasticpolyurethane includes a polyether segment (i.e., a segment having one ormore ether groups). Suitable polyethers include, but are not limited to,polyethylene oxide (PEO), polypropylene oxide (PPO), polytetrahydrofuran(PTHF), polytetramethylene oxide (PTMO), and combinations thereof. Theterm “alkyl” as used herein refers to straight chained and branchedsaturated hydrocarbon groups containing one to thirty carbon atoms, forexample, one to twenty carbon atoms, or one to ten carbon atoms. Theterm C_(n) means the alkyl group has “n” carbon atoms. For example, C₄alkyl refers to an alkyl group that has 4 carbon atoms. C₁₋₇alkyl refersto an alkyl group having a number of carbon atoms encompassing theentire range (i.e., 1 to 7 carbon atoms), as well as all subgroups(e.g., 1-6, 2-7, 1-5, 3-6, 1, 2, 3, 4, 5, 6, and 7 carbon atoms).Non-limiting examples of alkyl groups include, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl(1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unlessotherwise indicated, an alkyl group can be an unsubstituted alkyl groupor a substituted alkyl group.

In some examples of the thermoplastic polyurethane, the at least one R₂segment includes a polyester segment. The polyester segment can bederived from the polyesterification of one or more dihydric alcohols(e.g., ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol,1,4-butanediol, 1,3-butanediol, 2-methylpentanediol-1,5,diethyleneglycol,1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol,cyclohexanedimethanol, and combinations thereof) with one or moredicarboxylic acids (e.g., adipic acid, succinic acid, sebacic acid,suberic acid, methyladipic acid, glutaric acid, pimelic acid, azelaicacid, thiodipropionic acid and citraconic acid and combinationsthereof). The polyester also can be derived from polycarbonateprepolymers, such as poly(hexamethylene carbonate) glycol,poly(propylene carbonate) glycol, poly(tetramethylene carbonate)glycol,and poly(nonanemethylene carbonate) glycol. Suitable polyesters caninclude, for example, polyethylene adipate (PEA), poly(1,4-butyleneadipate), poly(tetramethylene adipate), poly(hexamethylene adipate),polycaprolactone, polyhexamethylene carbonate, poly(propylenecarbonate), poly(tetramethylene carbonate), poly(nonanemethylenecarbonate), and combinations thereof.

In various of the thermoplastic polyurethanes, at least one R₂ segmentincludes a polycarbonate segment. The polycarbonate segment can bederived from the reaction of one or more dihydric alcohols (e.g.,ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol,1,4-butanediol, 1,3-butanediol, 2-methylpentanediol-1,5, diethyleneglycol, 1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol,cyclohexanedimethanol, and combinations thereof) with ethylenecarbonate.

In various examples, the aliphatic group is linear and can include, forexample, a C₁₋₂₀ alkylene chain or a C₁₋₂₀ alkenylene chain (e.g.,methylene, ethylene, propylene, butylene, pentylene, hexylene,heptylene, octylene, nonylene, decylene, undecylene, dodecylene,tridecylene, ethenylene, propenylene, butenylene, pentenylene,hexenylene, heptenylene, octenylene, nonenylene, decenylene,undecenylene, dodecenylene, tridecenylene). The term “alkylene” refersto a bivalent hydrocarbon. The term Cn means the alkylene group has “n”carbon atoms. For example, C₁₋₆ alkylene refers to an alkylene grouphaving, e.g., 1, 2, 3, 4, 5, or 6 carbon atoms. The term “alkenylene”refers to a bivalent hydrocarbon having at least one double bond.

In various aspects, the aliphatic and aromatic groups can be substitutedwith one or more pendant relatively hydrophilic and/or charged groups.In some aspects, the pendant hydrophilic group includes one or more(e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) hydroxyl groups. In variousaspects, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) amino groups. In some cases, the pendanthydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10or more) carboxylate groups. For example, the aliphatic group caninclude one or more polyacrylic acid group. In some cases, the pendanthydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10or more) sulfonate groups. In some cases, the pendant hydrophilic groupincludes one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more)phosphate groups. In some examples, the pendant hydrophilic groupincludes one or more ammonium groups (e.g., tertiary and/or quaternaryammonium). In other examples, the pendant hydrophilic group includes oneor more zwitterionic groups (e.g., a betaine, such aspoly(carboxybetaine (pCB) and ammonium phosphonate groups such as aphosphatidylcholine group).

In some aspects, the R₂ segment can include charged groups that arecapable of binding to a counterion to ionically crosslink thethermoplastic polymer and form ionomers. In these aspects, for example,R₂ is an aliphatic or aromatic group having pendant amino, carboxylate,sulfonate, phosphate, ammonium, or zwitterionic groups, or combinationsthereof.

In various cases when a pendant hydrophilic group is present, thependant “hydrophilic” group is at least one polyether group, such as twopolyether groups. In other cases, the pendant hydrophilic group is atleast one polyester. In various cases, the pendant hydrophilic group ispolylactone group (e.g., polyvinylpyrrolidone). Each carbon atom of thependant hydrophilic group can optionally be substituted with, e.g., aC₁₋₆ alkyl group. In some of these aspects, the aliphatic and aromaticgroups can be graft polymeric groups, wherein the pendant groups arehomopolymeric groups (e.g., polyether groups, polyester groups,polyvinylpyrrolidone groups).

In some aspects, the pendant hydrophilic group is a polyether group(e.g., a polyethylene oxide group, a polyethylene glycol group), apolyvinylpyrrolidone group, a polyacrylic acid group, or combinationsthereof.

The pendant hydrophilic group can be bonded to the aliphatic group oraromatic group through a linker. The linker can be any bifunctionalsmall molecule (e.g., C₁₋₂₀) capable of linking the pendant hydrophilicgroup to the aliphatic or aromatic group. For example, the linker caninclude a diisocyanate group, as previously described herein, which whenlinked to the pendant hydrophilic group and to the aliphatic or aromaticgroup forms a carbamate bond. In some aspects, the linker can be4,4′-diphenylmethane diisocyanate (MDI), as shown below.

In some exemplary aspects, the pendant hydrophilic group is apolyethylene oxide group and the linking group is MDI, as shown below.

In some aspects, the pendant hydrophilic group is functionalized toenable it to bond to the aliphatic or aromatic group, optionally throughthe linker. In various aspects, for example, when the pendanthydrophilic group includes an alkene group, which can undergo a Michaeladdition with a sulfhydryl-containing bifunctional molecule (i.e., amolecule having a second reactive group, such as a hydroxyl group oramino group), to result in a hydrophilic group that can react with thepolymer backbone, optionally through the linker, using the secondreactive group. For example, when the pendant hydrophilic group is apolyvinylpyrrolidone group, it can react with the sulfhydryl group onmercaptoethanol to result in hydroxyl-functionalizedpolyvinylpyrrolidone, as shown below.

In some of the aspects disclosed herein, at least one R₂ segmentincludes a polytetramethylene oxide group. In other exemplary aspects,at least one R₂ segment can include an aliphatic polyol groupfunctionalized with a polyethylene oxide group or polyvinylpyrrolidonegroup, such as the polyols described in E.P. Patent No. 2 462 908, whichis hereby incorporated by reference. For example, the R₂ segment can bederived from the reaction product of a polyol (e.g., pentaerythritol or2,2,3-trihydroxypropanol) and either MDI-derivatized methoxypolyethyleneglycol (to obtain compounds as shown in Formulas 6 or 7) or withMDI-derivatized polyvinylpyrrolidone (to obtain compounds as shown inFormulas 8 or 9) that had been previously been reacted withmercaptoethanol, as shown below.

In various aspects, at least one R₂ is a polysiloxane, In these cases,R₂ can be derived from a silicone monomer of Formula 10, such as asilicone monomer disclosed in U.S. Pat. No. 5,969,076, which is herebyincorporated by reference:

wherein: a is 1 to 10 or larger (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or10); each R₄ independently is hydrogen, C₁₋₁₈ alkyl, C₂₋₁₈ alkenyl,aryl, or polyether; and each R₅ independently is C₁₋₁₀ alkylene,polyether, or polyurethane.

In some aspects, each R₄ independently is a H, C₁₋₁₀ alkyl, C₂₋₁₀alkenyl, C₁₋₆ aryl, polyethylene, polypropylene, or polybutylene group.For example, each R₄ can independently be selected from the groupconsisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,s-butyl, t-butyl, ethenyl, propenyl, phenyl, and polyethylene groups.

In various aspects, each R₅ independently includes a C₁₋₁₀ alkylenegroup (e.g., a methylene, ethylene, propylene, butylene, pentylene,hexylene, heptylene, octylene, nonylene, or decylene group). In othercases, each R₅ is a polyether group (e.g., a polyethylene,polypropylene, or polybutylene group). In various cases, each R₅ is apolyurethane group.

Optionally, in some aspects, the polyurethane can include an at leastpartially crosslinked polymeric network that includes polymer chainsthat are derivatives of polyurethane. In such cases, it is understoodthat the level of crosslinking is such that the polyurethane retainsthermoplastic properties (i.e., the crosslinked thermoplasticpolyurethane can be softened or melted and re-solidified under theprocessing conditions described herein). This crosslinked polymericnetwork can be produced by polymerizing one or more isocyanates with oneor more polyamino compounds, polysulfhydryl compounds, or combinationsthereof, as shown in Formulas 11 and 12, below:

wherein the variables are as described above. Additionally, theisocyanates can also be chain extended with one or more polyamino orpolythiol chain extenders to bridge two or more isocyanates, such aspreviously described for the polyurethanes of Formula 2.

As described herein, the thermoplastic polyurethane can be physicallycrosslinked through e.g., nonpolar or polar interactions between theurethane or carbamate groups on the polymers (the hard segments. Inthese aspects, component R₁ in Formula 1, and components R₁ and R₃ inFormula 2, forms the portion of the polymer often referred to as the“hard segment”, and component R₂ forms the portion of the polymer oftenreferred to as the “soft segment”. In these aspects, the soft segmentcan be covalently bonded to the hard segment. In some examples, thethermoplastic polyurethane having physically crosslinked hard and softsegments can be a hydrophilic thermoplastic polyurethane (i.e., athermoplastic polyurethane including hydrophilic groups as disclosedherein).

Thermoplastic Polyamides

In various aspects, the thermoplastic polymer can comprise athermoplastic polyamide. The thermoplastic polyamide can be a polyamidehomopolymer having repeating polyamide segments of the same chemicalstructure. Alternatively, the polyamide can comprise a number ofpolyamide segments having different polyamide chemical structures (e.g.,polyamide 6 segments, polyamide 11 segments, polyamide 12 segments,polyamide 66 segments, etc.). The polyamide segments having differentchemical structure can be arranged randomly, or can be arranged asrepeating blocks.

In aspects, the thermoplastic polymers can be a block co-polyamide. Forexample, the block co-polyamide can have repeating hard segments, andrepeating soft segments. The hard segments can comprise polyamidesegments, and the soft segments can comprise non-polyamide segments. Thethermoplastic polymers can be an elastomeric thermoplastic co-polyamidecomprising or consisting of block co-polyam ides having repeating hardsegments and repeating soft segments. In block co-polymers, includingblock co-polymers having repeating hard segments and soft segments,physical crosslinks can be present within the segments or between thesegments or both within and between the segments.

The thermoplastic polyamide can be a co-polyamide (i.e., a co-polymerincluding polyamide segments and non-polyamide segments). The polyamidesegments of the co-polyamide can comprise or consist of polyamide 6segments, polyamide 11 segments, polyamide 12 segments, polyamide 66segments, or any combination thereof. The polyamide segments of theco-polyamide can be arranged randomly, or can be arranged as repeatingsegments. In a particular example, the polyamide segments can compriseor consist of polyamide 6 segments, or polyamide 12 segments, or bothpolyamide 6 segment and polyamide 12 segments. In the example where thepolyamide segments of the co-polyamide include of polyamide 6 segmentsand polyamide 12 segments, the segments can be arranged randomly. Thenon-polyamide segments of the co-polyamide can comprise or consist ofpolyether segments, polyester segments, or both polyether segments andpolyester segments. The co-polyamide can be a co-polyamide, or can be arandom co-polyamide. The thermoplastic copolyamide can be formed fromthe polycodensation of a polyamide oligomer or prepolymer with a secondoligomer prepolymer to form a copolyamide (i.e., a co-polymer includingpolyamide segments. Optionally, the second prepolymer can be ahydrophilic prepolymer.

In some aspects, the thermoplastic polyamide itself, or the polyamidesegment of the thermoplastic copolyamide can be derived from thecondensation of polyamide prepolymers, such as lactams, amino acids,and/or diamino compounds with dicarboxylic acids, or activated formsthereof. The resulting polyamide segments include amide linkages(—(CO)NH—). The term “amino acid” refers to a molecule having at leastone amino group and at least one carboxyl group. Each polyamide segmentof the thermoplastic polyamide can be the same or different.

In some aspects, the thermoplastic polyamide or the polyamide segment ofthe thermoplastic copolyamide is derived from the polycondensation oflactams and/or amino acids, and includes an amide segment having astructure shown in Formula 13, below, wherein R₆ is the segment of thepolyamide derived from the lactam or amino acid.

In some aspects, R₆ is derived from a lactam. In some cases, R₆ isderived from a C₃₋₂₀ lactam, or a C₄₋₁₅ lactam, or a C₆₋₁₂ lactam. Forexample, R₆ can be derived from caprolactam or laurolactam. In somecases, R₆ is derived from one or more amino acids. In various cases, R₆is derived from a C₄₋₂₅ amino acid, or a C₅₋₂₀ amino acid, or a C₈₋₁₅amino acid. For example, R₆ can be derived from 12-aminolauric acid or11-aminoundecanoic acid.

Optionally, in order to increase the relative degree of hydrophilicityof the thermoplastic copolyamide, Formula 13 can include apolyamide-polyether block copolymer segment, as shown below:

wherein m is 3-20, and n is 1-8. In some exemplary aspects, m is 4-15,or 6-12 (e.g., 6, 7, 8, 9, 10, 11, or 12), and n is 1, 2, or 3. Forexample, m can be 11 or 12, and n can be 1 or 3. In various aspects, thethermoplastic polyamide or the polyamide segment of the thermoplasticco-polyamide is derived from the condensation of diamino compounds withdicarboxylic acids, or activated forms thereof, and includes an amidesegment having a structure shown in Formula 15, below, wherein R₇ is thesegment of the polyamide derived from the diamino compound, R₈ is thesegment derived from the dicarboxylic acid compound:

In some aspects, R₇ is derived from a diamino compound that includes analiphatic group having C₄₋₁₅ carbon atoms, or C₅₋₁₀ carbon atoms, orC₆₋₉ carbon atoms. In some aspects, the diamino compound includes anaromatic group, such as phenyl, naphthyl, xylyl, and tolyl. Suitablediamino compounds from which R₇ can be derived include, but are notlimited to, hexamethylene diamine (HMD), tetramethylene diamine,trimethyl hexamethylene diamine (TMD),m-xylylene diamine (MXD), and1,5-pentamine diamine. In various aspects, R₈ is derived from adicarboxylic acid or activated form thereof, includes an aliphatic grouphaving C₄₋₁₅ carbon atoms, or C₅₋₁₂ carbon atoms, or C₆₋₁₀ carbon atoms.In some cases, the dicarboxylic acid or activated form thereof fromwhich R₈ can be derived includes an aromatic group, such as phenyl,naphthyl, xylyl, and tolyl groups. Suitable carboxylic acids oractivated forms thereof from which R₈ can be derived include, but arenot limited to adipic acid, sebacic acid, terephthalic acid, andisophthalic acid. In some aspects, the polymer chains are substantiallyfree of aromatic groups.

In some aspects, each polyamide segment of the thermoplastic polyamide(including the thermoplastic copolyamide) is independently derived froma polyamide prepolymer selected from the group consisting of12-aminolauric acid, caprolactam, hexamethylene diamine and adipic acid.

In some aspects, the thermoplastic polyamide comprises or consists of athermoplastic poly(ether-block-amide). The thermoplasticpoly(ether-block-amide) can be formed from the polycondensation of acarboxylic acid terminated polyamide prepolymer and a hydroxylterminated polyether prepolymer to form a thermoplasticpoly(ether-block-amide), as shown in Formula 16:

In various aspects, a disclosed poly(ether block amide) polymer isprepared by polycondensation of polyamide blocks containing reactiveends with polyether blocks containing reactive ends. Examples include,but are not limited to: 1) polyamide blocks containing diamine chainends with polyoxyalkylene blocks containing carboxylic chain ends; 2)polyamide blocks containing dicarboxylic chain ends with polyoxyalkyleneblocks containing diamine chain ends obtained by cyanoethylation andhydrogenation of aliphatic dihydroxylated alpha-omega polyoxyalkylenesknown as polyether diols; 3) polyamide blocks containing dicarboxylicchain ends with polyether diols, the products obtained in thisparticular case being polyetheresteramides. The polyamide block of thethermoplastic poly(ether-block-amide) can be derived from lactams, aminoacids, and/or diamino compounds with dicarboxylic acids as previouslydescribed. The polyether block can be derived from one or morepolyethers selected from the group consisting of polyethylene oxide(PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof.

Disclosed poly(ether block amide) polymers include those comprisingpolyamide blocks comprising dicarboxylic chain ends derived from thecondensation of α, ω-aminocarboxylic acids, of lactams or ofdicarboxylic acids and diamines in the presence of a chain-limitingdicarboxylic acid. In poly(ether block amide) polymers of this type, aα, ω-aminocarboxylic acid such as aminoundecanoic acid can be used; alactam such as caprolactam or lauryllactam can be used; a dicarboxylicacid such as adipic acid, decanedioic acid or dodecanedioic acid can beused; and a diamine such as hexamethylenediamine can be used; or variouscombinations of any of the foregoing. In various aspects, the copolymercomprises polyamide blocks comprising polyamide 12 or of polyamide 6.

Disclosed poly(ether block amide) polymers include those comprisingpolyamide blocks derived from the condensation of one or more α,ω-aminocarboxylic acids and/or of one or more lactams containing from 6to 12 carbon atoms in the presence of a dicarboxylic acid containingfrom 4 to 12 carbon atoms, and are of low mass, i.e., they have an Mn offrom 400 to 1000. In poly(ether block amide) polymers of this type, a α,ω-aminocarboxylic acid such as aminoundecanoic acid or aminododecanoicacid can be used; a dicarboxylic acids such as adipic acid, sebacicacid, isophthalic acid, butanedioic acid, 1,4-cyclohexyldicarboxylicacid, terephthalic acid, the sodium or lithium salt of sulphoisophthalicacid, dimerized fatty acids (these dimerized fatty acids have a dimercontent of at least 98% and are preferably hydrogenated) anddodecanedioic acid HOOC—(CH2)10-COOH can be used; and a lactam such ascaprolactam and lauryllactam can be used; or various combinations of anyof the foregoing. In various aspects, the copolymer comprises polyamideblocks obtained by condensation of lauryllactam in the presence ofadipic acid or dodecanedioic acid and with a number average molecularweight of 750 have a melting point of 127-130 degrees C. In a furtheraspect, the various constituents of the polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C. and advantageously between 90 degrees C. and 135 degreesC.

Disclosed poly(ether block amide) polymers include those comprisingpolyamide blocks derived from the condensation of at least one α,ω-aminocarboxylic acid (or a lactam), at least one diamine and at leastone dicarboxylic acid. In copolymers of this type, a α,ω-aminocarboxylicacid, the lactam and the dicarboxylic acid can be chosen from thosedescribed herein above and the diamine such as an aliphatic diaminecontaining from 6 to 12 atoms and can be arylic and/or saturated cyclicsuch as, but not limited to, hexamethylenediamine, piperazine,1-aminoethylpiperazine, bisaminopropylpiperazine, tetramethylenediamine,octamethylene-diamine, decamethylenediamine, dodecamethylenediamine,1,5-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyols,isophoronediamine (IPD), methylpentamethylenediamine (MPDM),bis(aminocyclohexyl)methane (BACM) andbis(3-methyl-4-aminocyclohexyl)methane (BMACM) can be used.

In various aspects, the constituents of the polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C. and advantageously between 90 degrees C. and 135 degreesC. In a further aspect, the various constituents of the polyamide blockand their proportion can be chosen in order to obtain a melting point ofless than 150 degrees C. and advantageously between 90 degrees C. and135 degrees C.

In an aspect, the number average molar mass of the polyamide blocks canbe from about 300 grams per mole (g/mol) and about 15,000 g/mol, fromabout 500 g/mol and about 10,000 g/mol, from about 500 g/mol and about6,000 g/mol, from about 500 g/mol to 5,000 g/mol, and from about 600g/mol and about 5,000 g/mol. In a further aspect, the number averagemolecular weight of the polyether block can range from about 100 g/molto about 6,000 g/mol, from about 400 g/mol to 3000 g/mol and from about200 g/mol to about 3,000 g/mol. In a still further aspect, the polyether(PE) content (x) of the poly(ether block amide) polymer can be fromabout 0.05 to about 0.8 (i.e., from about 5 mole percent to about 80mole percent). In a yet further aspect, the polyether blocks can bepresent from about 10 weight percent to about 50 weight percent, fromabout 20 weight percent to about 40 weight percent, and from about 30weight percent to about 40 weight percent. The polyamide blocks can bepresent from about 50 weight percent to about 90 weight percent, fromabout 60 weight percent to about 80 weight percent, and from about 70weight percent to about 90 weight percent.

In an aspect, the polyether blocks can contain units other than ethyleneoxide units, such as, for example, propylene oxide orpolytetrahydrofuran (which leads to polytetramethylene glycolsequences). It is also possible to use simultaneously PEG blocks, i.e.those consisting of ethylene oxide units, PPG blocks, i.e. thoseconsisting of propylene oxide units, and PTMG blocks, i.e. thoseconsisting of tetramethylene glycol units, also known aspolytetrahydrofuran. PPG or PTMG blocks are advantageously used. Theamount of polyether blocks in these copolymers containing polyamide andpolyether blocks can be from about 10 weight percent to about 50 weightpercent of the copolymer and from about 35 weight percent to about 50weight percent.

The copolymers containing polyamide blocks and polyether blocks can beprepared by any means for attaching the polyamide blocks and thepolyether blocks. In practice, two processes are essentially used, onebeing a 2-step process and the other a one-step process.

In the two-step process, the polyamide blocks having dicarboxylic chainends are prepared first, and then, in a second step, these polyamideblocks are linked to the polyether blocks. The polyamide blocks havingdicarboxylic chain ends are derived from the condensation of polyamideprecursors in the presence of a chain-stopper dicarboxylic acid. If thepolyamide precursors are only lactams or α,ω-aminocarboxylic acids, adicarboxylic acid is added. If the precursors already comprise adicarboxylic acid, this is used in excess with respect to thestoichiometry of the diamines. The reaction usually takes place between180 and 300 degrees C., preferably 200 to 290 degrees C., and thepressure in the reactor is set between 5 and 30 bar and maintained forapproximately 2 to 3 hours. The pressure in the reactor is slowlyreduced to atmospheric pressure and then the excess water is distilledoff, for example for one or two hours.

Once the polyamide having carboxylic acid end groups has been prepared,the polyether, the polyol and a catalyst are then added. The totalamount of polyether can be divided and added in one or more portions, ascan the catalyst. In an aspect, the polyether is added first and thereaction of the OH end groups of the polyether and of the polyol withthe COOH end groups of the polyamide starts, with the formation of esterlinkages and the elimination of water. Water is removed as much aspossible from the reaction mixture by distillation and then the catalystis introduced in order to complete the linking of the polyamide blocksto the polyether blocks. This second step takes place with stirring,preferably under a vacuum of at least 50 millibar (5000 Pascals) at atemperature such that the reactants and the copolymers obtained are inthe molten state. By way of example, this temperature can be between 100and 400 degrees C. and usually between 200 and 250 degrees C. Thereaction is monitored by measuring the torque exerted by the polymermelt on the stirrer or by measuring the electric power consumed by thestirrer. The end of the reaction is determined by the value of thetorque or of the target power. The catalyst is defined as being anyproduct which promotes the linking of the polyamide blocks to thepolyether blocks by esterification. Advantageously, the catalyst is aderivative of a metal (M) chosen from the group formed by titanium,zirconium and hafnium. In an aspect, the derivative can be prepared froma tetraalkoxides consistent with the general formula M(OR)4, in which Mrepresents titanium, zirconium or hafnium and R, which can be identicalor different, represents linear or branched alkyl radicals having from 1to 24 carbon atoms.

In a further aspect, the catalyst can comprise a salt of the metal (M),particularly the salt of (M) and of an organic acid and the complexsalts of the oxide of (M) and/or the hydroxide of (M) and an organicacid. In a still further aspect, the organic acid can be formic acid,acetic acid, propionic acid, butyric acid, valeric acid, caproic acid,caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid,oleic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid,phenylacetic acid, benzoic acid, salicylic acid, oxalic acid, malonicacid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaricacid, phthalic acid and crotonic acid. Acetic and propionic acids areparticularly preferred. In some aspects, M is zirconium and such saltsare called zirconyl salts, e.g., the commercially available product soldunder the name zirconyl acetate.

In an aspect, the weight proportion of catalyst varies from about 0.01to about 5 percent of the weight of the mixture of the dicarboxylicpolyamide with the polyetherdiol and the polyol. In a further aspect,the weight proportion of catalyst varies from about 0.05 to about 2percent of the weight of the mixture of the dicarboxylic polyamide withthe polyetherdiol and the polyol.

In the one-step process, the polyamide precursors, the chain stopper andthe polyether are blended together; what is then obtained is a polymerhaving essentially polyether blocks and polyamide blocks of veryvariable length, but also the various reactants that have reactedrandomly, which are distributed randomly along the polymer chain. Theyare the same reactants and the same catalyst as in the two-step processdescribed above. If the polyamide precursors are only lactams, it isadvantageous to add a little water. The copolymer has essentially thesame polyether blocks and the same polyamide blocks, but also a smallportion of the various reactants that have reacted randomly, which aredistributed randomly along the polymer chain. As in the first step ofthe two-step process described above, the reactor is closed and heated,with stirring. The pressure established is between 5 and 30 bar. Whenthe pressure no longer changes, the reactor is put under reducedpressure while still maintaining vigorous stirring of the moltenreactants. The reaction is monitored as previously in the case of thetwo-step process.

The proper ratio of polyamide to polyether blocks can be found in asingle poly(ether block amide), or a blend of two or more differentcomposition poly(ether block amide)s can be used with the proper averagecomposition. In one aspect, it can be useful to blend a block copolymerhaving a high level of polyamide groups with a block copolymer having ahigher level of polyether blocks, to produce a blend having an averagelevel of polyether blocks of about 20 to 40 weight percent of the totalblend of poly(amid-block-ether) copolymers, and preferably about 30 to35 weight percent. In a further aspect, the copolymer comprises a blendof two different poly(ether-block-amide)s comprising at least one blockcopolymer having a level of polyether blocks below about 35 weightpercent, and a second poly(ether-block-amide) having at least about 45weight percent of polyether blocks.

Exemplary commercially available copolymers include, but are not limitedto, those available under the tradenames of VESTAMID (EvonikIndustries); PLATAMID (Arkema), e.g., product code H2694; PEBAX(Arkema), e.g., product code “PEBAX MH1657” and “PEBAX MV1074”; PEBAXRNEW (Arkema); GRILAMID (EMS-Chemie AG), or also to other similarmaterials produced by various other suppliers.

In some aspects, the thermoplastic polyamide is physically crosslinkedthrough, e.g., nonpolar or polar interactions between the polyamidegroups of the polymers. In examples where the thermoplastic polyamide isa thermoplastic copolyamide, the thermoplastic copolyamide can bephysically crosslinked through interactions between the polyamidegroups, an optionally by interactions between the copolymer groups. Whenthe thermoplastic copolyamide is physically crosslinked thoroughinteractions between the polyamide groups, the polyamide segments canform the portion of the polymer referred to as the “hard segment”, andcopolymer segments can form the portion of the polymer referred to asthe “soft segment”. For example, when the thermoplastic copolyamide is athermoplastic poly(ether-block-amide), the polyamide segments form thehard segment portion of the polymer, and polyether segments can form thesoft segment portion of the polymer. Therefore, in some examples, thethermoplastic polymer can include a physically crosslinked polymericnetwork having one or more polymer chains with amide linkages.

In some aspects, the polyamide segment of the thermoplastic co-polyamideincludes polyamide-11 or polyamide-12 and the polyether segment is asegment selected from the group consisting of polyethylene oxide,polypropylene oxide, and polytetramethylene oxide segments, andcombinations thereof.

Optionally, the thermoplastic polyamide can be partially covalentlycrosslinked, as previously described herein. In such cases, it is to beunderstood that the degree of crosslinking present in the thermoplasticpolyamide is such that, when it is thermally processed in the form of ayarn or fiber to form the articles of footwear of the presentdisclosure, the partially covalently crosslinked thermoplastic polyamideretains sufficient thermoplastic character that the partially covalentlycrosslinked thermoplastic polyamide is softened or melted during theprocessing and re-solidifies.

Thermoplastic Polyesters

In aspects, the thermoplastic polymers can comprise a thermoplasticpolyester. The thermoplastic polyester can be formed by reaction of oneor more carboxylic acids, or its ester-forming derivatives, with one ormore bivalent or multivalent aliphatic, alicyclic, aromatic oraraliphatic alcohols or a bisphenol. The thermoplastic polyester can bea polyester homopolymer having repeating polyester segments of the samechemical structure. Alternatively, the polyester can comprise a numberof polyester segments having different polyester chemical structures(e.g., polyglycolic acid segments, polylactic acid segments,polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, etc.). The polyester segments havingdifferent chemical structure can be arranged randomly, or can bearranged as repeating blocks.

Exemplary carboxylic acids that can be used to prepare a thermoplasticpolyester include, but are not limited to, adipic acid, pimelic acid,suberic acid, azelaic acid, sebacic acid, nonane dicarboxylic acid,decane dicarboxylic acid, undecane dicarboxylic acid, terephthalic acid,isophthalic acid, alkyl-substituted or halogenated terephthalic acid,alkyl-substituted or halogenated isophthalic acid, nitro-terephthalicacid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl thioetherdicarboxylic acid, 4,4′-diphenyl sulfone-dicarboxylic acid,4,4′-diphenyl alkylenedicarboxylic acid, naphthalene-2,6-dicarboxylicacid, cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylicacid. Exemplary diols or phenols suitable for the preparation of thethermoplastic polyester include, but are not limited to, ethyleneglycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol,1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,2-propanediol,2,2-dimethyl-1,3-propanediol, 2,2,4-trimethylhexanediol, p-xylenediol,1,4-cyclohexanediol, 1,4-cyclohexane dimethanol, and bis-phenol A.

In some aspects, the thermoplastic polyester is a polybutyleneterephthalate (PBT), a polytrimethylene terephthalate, apolyhexamethylene terephthalate, a poly-1,4-dimethylcyclohexaneterephthalate, a polyethylene terephthalate (PET), a polyethyleneisophthalate (PEI), a polyarylate (PAR), a polybutylene naphthalate(PBN), a liquid crystal polyester, or a blend or mixture of two or moreof the foregoing.

The thermoplastic polyester can be a co-polyester (i.e., a co-polymerincluding polyester segments and non-polyester segments). Theco-polyester can be an aliphatic co-polyester (i.e., a co-polyester inwhich both the polyester segments and the non-polyester segments arealiphatic). Alternatively, the co-polyester can include aromaticsegments. The polyester segments of the co-polyester can comprise orconsist of polyglycolic acid segments, polylactic acid segments,polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, or any combination thereof. The polyestersegments of the co-polyester can be arranged randomly, or can bearranged as repeating blocks.

For example, the thermoplastic polyester can be a block co-polyesterhaving repeating blocks of polymeric units of the same chemicalstructure (segments) which are relatively harder (hard segments), andrepeating blocks of polymeric segments which are relatively softer (softsegments). In block co-polyesters, including block co-polyesters havingrepeating hard segments and soft segments, physical crosslinks can bepresent within the blocks or between the blocks or both within andbetween the blocks. In a particular example, the thermoplastic materialcan comprise or consist essentially of an elastomeric thermoplasticco-polyester having repeating blocks of hard segments and repeatingblocks of soft segments.

The non-polyester segments of the co-polyester can comprise or consistof polyether segments, polyamide segments, or both polyether segmentsand polyamide segments. The co-polyester can be a block co-polyester, orcan be a random co-polyester. The thermoplastic co-polyester can beformed from the polycodensation of a polyester oligomer or prepolymerwith a second oligomer prepolymer to form a block copolyester.Optionally, the second prepolymer can be a hydrophilic prepolymer. Forexample, the co-polyester can be formed from the polycondensation ofterephthalic acid or naphthalene dicarboxylic acid with ethylene glycol,1,4-butanediol, or 1-3 propanediol. Examples of co-polyesters includepolyethelene adipate, polybutylene succinate,poly(3-hydroxbutyrate-co-3-hydroxyvalerate), polyethylene terephthalate,polybutylene terephthalate, polytrimethylene terephthalate, polyethylenenapthalate, and combinations thereof. In a particular example, theco-polyamide can comprise or consist of polyethylene terephthalate.

In some aspects, the thermoplastic polyester is a block copolymercomprising segments of one or more of polybutylene terephthalate (PBT),a polytrimethylene terephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), and a liquid crystal polyester. Forexample, a suitable thermoplastic polyester that is a block copolymercan be a PET/PEI copolymer, a polybutylene terephthalate/tetraethyleneglycol copolymer, a polyoxyalkylenediimide diacid/polybutyleneterephthalate copolymer, or a blend or mixture of any of the foregoing.

In some aspects, the thermoplastic polyester is a biodegradable resin,for example, a copolymerized polyester in which poly(a-hydroxy acid)such as polyglycolic acid or polylactic acid is contained as principalrepeating units.

The disclosed thermoplastic polyesters can be prepared by a variety ofpolycondensation methods known to the skilled artisan, such as a solventpolymerization or a melt polymerization process.

Thermoplastic Polyolefins

In some aspects, the thermoplastic polymers can comprise or consistessentially of a thermoplastic polyolefin. Exemplary of thermoplasticpolyolefins useful can include, but are not limited to, polyethylene,polypropylene, and thermoplastic olefin elastomers (e.g.,metallocene-catalyzed block copolymers of ethylene and α-olefins having4 to about 8 carbon atoms). In a further aspect, the thermoplasticpolyolefin is a polymer comprising a polyethylene, an ethylene-α-olefincopolymer, an ethylene-propylene rubber (EPDM), a polybutene, apolyisobutylene, a poly-4-methylpent-1-ene, a polyisoprene, apolybutadiene, a ethylene-methacrylic acid copolymer, and an olefinelastomer such as a dynamically cross-linked polymer obtained frompolypropylene (PP) and an ethylene-propylene rubber (EPDM), and blendsor mixtures of the foregoing. Further exemplary thermoplasticpolyolefins useful in the disclosed compositions, yarns, and fibers arepolymers of cycloolefins such as cyclopentene or norbornene.

It is to be understood that polyethylene, which optionally can becrosslinked, is inclusive a variety of polyethylenes, including, but notlimited to, low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE), medium density polyethylene(MDPE), high density polyethylene (HDPE), high density and highmolecular weight polyethylene (HDPE-HMW), high density and ultrahighmolecular weight polyethylene (HDPE-UHMW), and blends or mixtures of anythe foregoing polyethylenes. A polyethylene can also be a polyethylenecopolymer derived from monomers of monolefins and diolefinscopolymerized with a vinyl, acrylic acid, methacrylic acid, ethylacrylate, vinyl alcohol, and/or vinyl acetate. Polyolefin copolymerscomprising vinyl acetate-derived units can be a high vinyl acetatecontent copolymer, e.g., greater than about 50 weight percent vinylacetate-derived composition.

In some aspects, the thermoplastic polyolefin, as disclosed herein, canbe formed through free radical, cationic, and/or anionic polymerizationby methods well known to those skilled in the art (e.g., using aperoxide initiator, heat, and/or light). In a further aspect, thedisclosed thermoplastic polyolefin can be prepared by radicalpolymerization under high pressure and at elevated temperature.Alternatively, the thermoplastic polyolefin can be prepared by catalyticpolymerization using a catalyst that normally contains one or moremetals from group IVb, Vb, VIb or VIII metals. The catalyst usually hasone or more than one ligand, typically oxides, halides, alcoholates,esters, ethers, amines, alkyls, alkenyls and/or aryls that can be eitherp- or s-coordinated complexed with the group IVb, Vb, VIb or VIII metal.In various aspects, the metal complexes can be in the free form or fixedon substrates, typically on activated magnesium chloride, titanium(III)chloride, alumina or silicon oxide. It is understood that the metalcatalysts can be soluble or insoluble in the polymerization medium. Thecatalysts can be used by themselves in the polymerization or furtheractivators can be used, typically a group Ia, IIa and/or IIIa metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes. The activators can be modified conveniently with furtherester, ether, amine or silyl ether groups.

Suitable thermoplastic polyolefins can be prepared by polymerization ofmonomers of monolefins and diolefins as described herein. Exemplarymonomers that can be used to prepare disclosed thermoplastic polyolefininclude, but are not limited to, ethylene, propylene, 1-butene,1-pentene, 1-hexene, 2-methyl-1-propene, 3-methyl-1-pentene,4-methyl-1-pentene, 5-methyl-1-hexene and mixtures thereof.

Suitable ethylene-α-olefin copolymers can be obtained bycopolymerization of ethylene with an α-olefin such as propylene,butene-1, hexene-1, octene-1,4-methyl-1-pentene or the like havingcarbon numbers of 3 to 12.

Suitable dynamically cross-linked polymers can be obtained bycross-linking a rubber component as a soft segment while at the sametime physically dispersing a hard segment such as PP and a soft segmentsuch as EPDM by using a kneading machine such as a Banbury mixer and abiaxial extruder.

In some aspects, the thermoplastic polyolefin can be a mixture ofthermoplastic polyolefins, such as a mixture of two or more polyolefinsdisclosed herein above. For example, a suitable mixture of thermoplasticpolyolefins can be a mixture of polypropylene with polyisobutylene,polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) ormixtures of different types of polyethylene (for example LDPE/HDPE).

In some aspects, the thermoplastic polyolefin can be a copolymer ofsuitable monolefin monomers or a copolymer of a suitable monolefinmonomer and a vinyl monomer. Exemplary thermoplastic polyolefincopolymers include, but are not limited to, ethylene/propylenecopolymers, linear low density polyethylene (LLDPE) and mixtures thereofwith low density polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyam ides.

In some aspects, the thermoplastic polyolefin can be a polypropylenehomopolymer, a polypropylene copolymers, a polypropylene randomcopolymer, a polypropylene block copolymer, a polyethylene homopolymer,a polyethylene random copolymer, a polyethylene block copolymer, a lowdensity polyethylene (LDPE), a linear low density polyethylene (LLDPE),a medium density polyethylene, a high density polyethylene (HDPE), orblends or mixtures of one or more of the preceding polymers.

In some aspects, the polyolefin is a polypropylene. The term“polypropylene,” as used herein, is intended to encompass any polymericcomposition comprising propylene monomers, either alone or in mixture orcopolymer with other randomly selected and oriented polyolefins, dienes,or other monomers (such as ethylene, butylene, and the like). Such aterm also encompasses any different configuration and arrangement of theconstituent monomers (such as atactic, syndiotactic, isotactic, and thelike). Thus, the term as applied to fibers is intended to encompassactual long strands, tapes, threads, and the like, of drawn polymer. Thepolypropylene can be of any standard melt flow (by testing); however,standard fiber grade polypropylene resins possess ranges of Melt FlowIndices between about 1 and 1000.

In some aspects, the polyolefin is a polyethylene. The term“polyethylene,” as used herein, is intended to encompass any polymericcomposition comprising ethylene monomers, either alone or in mixture orcopolymer with other randomly selected and oriented polyolefins, dienes,or other monomers (such as propylene, butylene, and the like). Such aterm also encompasses any different configuration and arrangement of theconstituent monomers (such as atactic, syndiotactic, isotactic, and thelike). Thus, the term as applied to fibers is intended to encompassactual long strands, tapes, threads, and the like, of drawn polymer. Thepolyethylene can be of any standard melt flow (by testing); however,standard fiber grade polyethylene resins possess ranges of Melt FlowIndices between about 1 and 1000.

Commercially-available thermoplastic polyimide hydrogels suitable forthe present aspects include those under the tradename “PEBAX” (e.g.,“PEBAX MH1657” and “PEBAX MV1074” from Arkema, Inc., Clear Lake, Tex.),and “SERENE” coating (Sumedics, Eden Prairie, Minn.). Suitablecommercially-available polyolefin materials include, but are not limitedto the “POLYOX” product line by Dow Chemical, Midland Mich., andstyrenic block co-polymers. Commercially-available styrenic co-polymersinclude, but are not limited to TPE-s (e.g., styrene-butadiene-styrene(SBS) block copolymers, such as “SOFPRENE” andstyrene-ethylene-butylene-styrene (SEBS) block copolymer, such as“LAPRENE”, by SO.F.TER. GROUP, Lebanon, Tenn.); thermoplasticcopolyester elastomers (e.g., thermoplastic elastomer vulcanizates(TPE-v or TPV)), such as “FORPRENE” by SO.F.TER. GROUP), “TERMOTON-V” byTermopol, Istanbul Turkey, and TPE block copolymers, such as“SANTOPRENE” (ExxonMobil, Irving, Tex.).

According to some aspects, the second polymeric material and/or thirdpolymeric material can further comprise, consist of, or consistessentially of one or more processing aids. These processing aids can beindependently selected from the group including, but not limited to,curing agents, initiators, plasticizers, mold release agents,lubricants, antioxidants, flame retardants, dyes, pigments, reinforcingand non-reinforcing fillers, fiber reinforcements, and lightstabilizers.

The outsole of the finished article of footwear in the presentdisclosure alternatively can be characterized based on its structure.For example, the outsole can be described, without limitation, accordingto the thickness or dimensions of the hydrogel located on theexternally-facing surface of the surface of the outsole, according tothe way the layered film is arranged in the finished article offootwear, according to the number of traction elements that are present,or according to whether or not the outsole is affixed to an upper thatcomprises a single piece or multiple pieces. According to an aspect, theoutsole has an externally-facing surface that is comprised, at least inpart, by the hydrogel material. The externally-facing surface of theoutsole can comprise from at least 10 percent, at least 25 percent, atleast 50 percent, at least 70 percent, at least 80 percent, or betweenabout 5 percent and about 95 percent hydrogel, based on the totalsurface area of the externally-facing surface of the outsole. Theoutsole can further comprise one or more traction elements present onits externally-facing surface.

According to another aspect of the present disclosure, the outsoleexhibits a “dry-state” thickness that is in the range of about 0.1millimeter (mm) to about 9.0 mm. Alternatively, the dry-state thicknessof the outsole is about 0.2 mm to about 5.0 mm; alternatively, about 0.2mm to about 2.0 mm. The hydration and swelling of the hydrogel can beobserved by an increase in the thickness of the outsole from thedry-state thickness, through a range of intermediate-state thicknessesas they hydrogel is hydrated, and finally to a saturated-statethickness, which is an average thickness of the outsole when hydrogel isfully saturated with water. For example, the saturated-state thicknessfor the fully-saturated outsole can be greater than 150 percent, greaterthan 200 percent, greater than 250 percent, greater than 300 percent,greater than 350 percent, greater than 400 percent, or greater than 500percent, of the dry-state thickness of the outsole.

The dry and wet states of the hydrogel in the outsole may allow thearticle of footwear to dynamically adapt in durability to account fordry and wet surface play. For example, when used on a dry ground, thehydrogel can be substantially dry, in which condition the hydrogel isrelatively stiffer and more wear resistant. Alternatively, when used onwet ground or when wet material is present on dry ground, the hydrogelcan quickly take up water to achieve a hydrated or fully saturatedcondition, in which condition the hydrogel material can be in a swollenand/or relatively compliant state. However, the wet ground imposes lesswear on the swollen and compliant hydrogel as compared to dry ground. Assuch, the outsole can be used in a variety of conditions, as desired.Nonetheless, the articles of footwear are particularly beneficial foruse in wet environments, such as with muddy surfaces, grass surfaces,and the like.

The outsole can be directly secured or otherwise operably secured to theupper using any suitable mechanism or method. As used herein, the terms“operably secured to”, such as for an outsole that is operably securedto an upper, refers collectively to direct connections, indirectconnections, integral formations, and combinations thereof. Forinstance, for an outsole that is operably secured to an upper, theoutsole can be directly connected to the upper (e.g., adhered directlythereto or glued with a cement, a primer, or an adhesive), can beintegrally formed with the upper (e.g., as a unitary component), andcombinations thereof.

The upper of the footwear has a body, which can be fabricated frommaterials known in the art for making articles of footwear, and isconfigured to receive a user's foot. The upper of a shoe consists of allcomponents of the shoe above the outsole. The different components ofthe upper can include a toe box; heal counter; and an Achilles notch, toname a few. These components are attached by stitches or more likelymolded to become a single unit to which the outsole is attached.

The upper or components of the upper usually comprise a soft body madeup of one or more lightweight materials. The materials used in the upperprovide stability, comfort, and a secure fit. For example, the upper canbe made from or include one or more components made from one or more ofnatural or synthetic leather, a thermoset polymer, a thermoplasticpolymer, or a mixture thereof. When desirable, the upper can be madeusing one of these components as a fabric or textile formed therefrom.

The textile can include; a knit, braided, woven, or nonwoven textilemade in whole or in part of a natural fiber; a knit, braided, woven ornon-woven textile made in whole or in part of a synthetic polymer, afilm of a synthetic polymer, etc.; and combinations thereof. The textilecan include one or more natural or synthetic fibers or yarns. Thesynthetic yarns can comprise, consist of, or consist essentially ofthermoplastic polyurethane (TPU), polyamide (e.g., “NYLON” etc.),polyester (e.g., polyethylene terephthalate or PET), polyolefin, or amixture thereof.

The upper and components of the upper can be manufactured according toconventional techniques (e.g., molding, extrusion, thermoforming,stitching, knitting, etc.). While illustrated in FIGS. 3B and 3D as ageneric design, the upper 85 can alternatively have any desiredaesthetic design, functional design, brand designators, or the like.

Still referring to FIG. 3D, the upper 85 can further comprise laces,flaps, straps, or other securing or foot engagement structures 90 usedto securely hold the shoe 80 to a wearer's foot. A tongue member,bootie, or other similar type structure can be provided in or near theshoe instep area in order to increase comfort and/or to moderate thepressure or feel applied to the wearer's foot by any foot engagementstructures 95.

When desirable, at least a portion of the upper 85 of the article offootwear, and in some aspects substantially the entirety of the upper,can be formed of a knitted component. Thus, the textile can be a knittextile with a circular knit textile being one specific example thereof.The knitted component can additionally or alternatively form anotherelement of the article of footwear 80 such as the insole, for example.

The knitted component can have a first side forming an inner surface ofthe upper (e.g., facing the void of the article of footwear) and asecond side forming an outer surface of the upper. An upper includingthe knitted component can substantially surround the void in order tosubstantially encompass the foot of a person when the article offootwear is in use. The first side and the second side of the knittedcomponent can exhibit different characteristics (e.g., the first sidecan provide abrasion resistance and comfort while the second side can berelatively rigid and provide water resistance). The knitted componentcan be formed as an integral one-piece element during a knittingprocess, such as a weft knitting process (e.g., with a flat knittingmachine or circular knitting machine), a warp knitting process, or anyother suitable knitting process. That is, the knitting process cansubstantially form the knit structure of the knitted component withoutthe need for significant post-knitting processes or steps.Alternatively, two or more portions of the knitted component can beformed separately and then attached. In some aspects, the knittedcomponent can be shaped after the knitting process to form and retainthe desired shape of the upper (for example, by using a foot-shapedlast). The shaping process can include attaching the knitted componentto another object (e.g., a strobel) and/or attaching one portion of theknitted component to another portion of the knitted component at a seamby sewing, by using an adhesive, or by another suitable attachmentprocess.

Forming the upper with the knitted component can provide the upper withadvantageous characteristics including, but not limited to, a particulardegree of elasticity (for example, as expressed in terms of Young'smodulus), breathability, bendability, strength, moisture absorption,weight, and abrasion resistance. These characteristics can beaccomplished by selecting a particular single layer or multi-layer knitstructure (e.g., a ribbed knit structure, a single jersey knitstructure, or a double jersey knit structure), by varying the size andtension of the knit structure, by using one or more yarns formed of aparticular material (e.g., a polyester material, a monofilamentmaterial, or an elastic material such as spandex), by selecting yarns ofa particular size (e.g., denier), or a combination thereof. The knittedcomponent can also provide desirable aesthetic characteristics byincorporating yarns having different colors or other visual propertiesarranged in a particular pattern. The yarns and/or the knit structure ofthe knitted component can be varied at different locations such that theknitted component has two or more portions with different properties(e.g., a portion forming the throat area of the upper can be relativelyelastic while another portion can be relatively inelastic). In someaspects, the knitted component can incorporate one or more materialswith properties that change in response to a stimulus (e.g.,temperature, moisture, electrical current, magnetic field, or light).For example, the knitted component can include yarns formed of apolymeric material (e.g., polyurethanes, polyamides, polyolefins, andnylons) that transitions from a solid state to a softened or liquidstate when subjected to certain temperatures at or above its meltingpoint and then transitions back to the solid state when cooled. Thepolymeric material can provide the ability to heat and then cool aportion of the knitted component to thereby form an area of bonded orcontinuous material that exhibits certain advantageous propertiesincluding a relatively high degree of rigidity, strength, and waterresistance, for example.

In some aspects, the knitted component can include one or more yarns orstrands that are at least partially inlaid or otherwise inserted withinthe knit structure of the knitted component during or after the knittingprocess, herein referred to as “tensile strands.” The tensile strandscan be substantially inelastic so as to have a substantially fixedlength. The tensile strands can extend through a plurality of courses ofthe knitted component or through a passage within the knitted componentand may limit the stretch of the knitted component in at least onedirection. For example, the tensile strands can extend approximatelyfrom a bite line of the upper to a throat area of the upper to limit thestretch of the upper in the lateral direction. The tensile strands canform one or more lace apertures for receiving a lace and/or can extendaround at least a portion of a lace aperture formed in the knitstructure of the knitted component.

When desirable, the article of footwear can further include the use ofan adhesive, a primer, or a combination thereof located between theoutsole and the upper attached thereto. The adhesive or primer cancomprise, but not be limited to, an epoxy, urethane, acrylic,cyanoacrylate, silicone, or a combination thereof.

According to various aspects, at least a portion of the external surfaceof the outsole can comprise a pattern or a texture. When desirable, thispattern can represent a tread pattern. In some aspects, the externalsurface of the outsole comprises one or more traction elements (as shownin FIGS. 2(A-B) and 3(A-D)) wherein the portion of said tractionelements that contact the ground are substantially free of the hydrogelmaterial. In aspects, the traction elements comprise a material that isharder than the hydrogel material. In some aspects, the one or moretraction elements can have a conical or rectangular shape as furtherdescribed below. The traction elements can provide enhanced tractionbetween the outsole and the ground. The traction elements also canprovide support or flexibility to the outsole and/or provide anaesthetic design or look to the footwear article.

According to the various aspects, the traction elements can include, butare not limited to, various shaped projections, such as cleats, studs,spikes, or similar elements configured to enhance traction between theoutsole and the ground for a wearer during cutting, turning, stopping,accelerating, and backward movement. According to the aspects, thetraction elements can be arranged in any necessary or desirable patternalong the bottom surface of the outsole. For instance, the tractionelements can be distributed in groups or clusters along the outsole(e.g., clusters of 2-8 traction elements). In certain aspects, thetraction elements can be arranged along the outsole symmetrically ornon-symmetrically between a medial side and a lateral side of thearticle of footwear. In certain aspects, one or more of the tractionelements can be arranged along a centerline of the outsole between themedial side and the lateral side.

According to some aspects, the traction elements can be made of one ormore materials that are different from the hydrogel, the secondpolymeric material, the third polymeric material, or the fourthpolymeric material that comprises the outsole. In some aspects, one ormore of the traction elements can comprise the same material as thesecond, third, or fourth polymeric materials. In some aspects, one ormore of the traction elements comprise the second polymeric material,third polymeric material, or fourth polymeric material and can be formedintegrally with the outsole during the molding steps as described in themethods of manufacturing the outsole defined herein. In yet otheraspects, at least one of the traction elements can be substantially freeof the second, third, or fourth polymeric materials. In some aspects,the one or more traction elements are made of a material that is harderthan the second, third, or fourth polymeric materials.

For example, in certain aspects the traction elements can include one ormore of polymeric materials such as thermoplastic elastomers; thermosetpolymers; elastomeric polymers; silicone polymers; natural and syntheticrubbers; composite materials including polymers reinforced with carbonfiber and/or glass; natural leather; metals such as aluminum, steel andthe like; and combinations thereof. In some aspects, the tractionelements are integrally formed with the outsole (e.g., molded together),the traction elements can include the same materials as the component(e.g., thermoplastic or thermoset materials). In some aspects, thetraction elements are separately provided (i.e., not molded with theoutsole) and can be otherwise operably coupled with the outsole. Forexample, the outsole can contain certain fittings or receptacles orreceiving holes with which the traction elements can be coupled. Inthese aspects the traction elements can comprise any suitable materialsthat can secured in the receiving holes of the outsole (e.g., metals andpolymeric materials) either as snap-fit, screw-on, or the like.

In some aspects, the traction elements can each independently have anynecessary or desired dimension (e.g., shape and size). Examples ofshapes for the traction elements include rectangular, hexagonal,cylindrical, conical, circular, square, triangular, trapezoidal,diamond, ovoid, as well as other regular or irregular shapes (e.g.,curved lines, C-shapes, etc.). In some aspects, the traction elementscan have the same or different heights, widths, and/or thicknesses aseach other. Further examples of suitable dimensions for the tractionelements and their arrangements along the outsole include those providedin soccer/global football footwear commercially available under thetradenames “TIEMPO”, “HYPERVENOM”, “MAGISTA”, and “MERCURIAL” from Nike,Inc. of Beaverton, Oreg.

In various aspects, the traction elements can be incorporated into theoutsole by any necessary or desired mechanism such that the tractionelements extend from the bottom surface of the outsole. In some aspects,the traction elements can be integrally formed with the outsole througha molding process. In some aspects, the outsole can be configured toreceive removable traction elements, such as screw-in or snap-intraction elements. In these aspects, the outsole can include receivingholes (e.g., threaded or snap-fit holes) or fittings, and the tractionelements can be screwed or snapped into or otherwise coupled with thereceiving holes or fittings to secure the traction elements to theoutsole.

In further aspects, a first portion of the traction elements can beintegrally formed with the outsole and a second portion of the tractionelements can be secured with screw-in, snap-in, or other similarmechanisms. The traction elements can also be configured as short studsfor use with artificial ground (AG) footwear, if desired. In someaspects, the receiving holes or fittings can be raised or otherwiseprotrude from the general plane of the external surface of the outsole.In some aspects, the receiving holes can be flush with the externalsurface. In some aspects, the outsole can comprise a combination ofthese features and elements.

According to various aspects, the one or more traction elements have alength (the dimension by which it protrudes from the externally-facingsurface of the outsole) that is greater than the hydrated orsaturated-state thickness of the outsole. The materials present in theoutsole and its corresponding dry and saturated thicknesses can beselected to ensure that the traction elements continue to provideground-engaging traction during use of the footwear, even when thehydrogel is in a fully swollen state. For example, the outsole can becharacterized by a “clearance” which is the difference between thelength of one or more traction elements and the thickness of the outsole(in its dry state, hydrated state, or saturated state). In some aspects,the average clearance for the saturated-state of the outsole isdesirably at least 8 millimeters (mm). In some aspects, the averageclearance of the outsole in its saturated state can be at least 9 mm, atleast 10 mm, or more.

Since the outsole is the outer most sole of the shoe it is directlyexposed to abrasion and wear. In some aspects, various portions of theoutsole can be constructed with different thickness and can exhibitdifferent degrees of flexibility. The outsole can comprise materialsthat are selected to provide necessary or desired properties, such as adegree of waterproofing, durability, and/or a coefficient of frictionthat is high enough to prevent slipping. In some cases, two or morematerials of different densities can be incorporated into the outsole togive a hardwearing outer surface. In some aspects, the hardwearingoutsole can be combined with a softer, more flexible midsole for greatercomfort. For example, the midsole can comprise a foam material formed assheet stock, by injection molding, or by compression molding. In someaspects, the foam material can be, without limitation, a polyurethane(PU), an ethylene vinyl acetate (EVA), a rubber, or a combinationthereof.

In some aspects, the article of footwear or shoe can also include aplatform upon which the foot will rest and that separates the upper fromthe foot of the person wearing the shoe. This platform is typically aseparate removable board called an insole (not shown) that is made ofcellulose or other materials, such as thermoplastic or thermosetelastomers, capable of providing a cushion between the ground and thefoot of the person wearing the shoe. The insole can be treated withadditives to inhibit bacterial growth. When desirable, the insole can beincorporated with, e.g., sewn into, the upper.

Referring once again to FIGS. 3B and 3D, in aspects the outsole 65 ofthe shoe 80 can be engaged with or attached to the upper 85, such as bybeing directly adhered thereto. In some aspects, at least a portion ofthe outsole can be attached to the upper 85 through the use ofadditional means conventionally known or used in the construction offootwear 80, such as through the use of cements or adhesives, bymechanical connectors, and by sewing or stitching, to name a few.

According to another aspect of the present disclosure, the use of anoutsole compositionally comprising a hydrogel on the external orground-facing surface is described. This use involves incorporating theoutsole as an externally-facing surface in a finished article offootwear in order to prevent or reduce soil accumulation on the outsoleand article. In some aspects, the outsole component or article retainsat least 5 percent less soil by weight; alternatively, at least 10percent less soil by weight, as compared to a conventional component orarticle that is similar except that the externally facing surface of theconventional component or article is substantially free of the hydrogel.

The following specific examples are given to illustrate the samplingprocedures and the test methods used to measure the properties exhibitedby the outsoles formed according to the teachings of the presentdisclosure. These specific examples should not be construed in a waythat limits the scope of the disclosure. Those skilled-in-the-art, inlight of the present disclosure, will appreciate that many changes canbe made in the specific embodiments which are disclosed herein and stillobtain alike or similar result without departing from or exceeding thespirit or scope of the disclosure. One skilled in the art will furtherunderstand that any properties reported herein represent properties thatare routinely measured and can be obtained by multiple differentmethods. The methods described herein represent one such method andother methods may be utilized without exceeding the scope of the presentdisclosure.

Example 1—Sampling Procedures

The predetermined sampling procedure can be a Component SamplingProcedure, when the component is present as an outsole component or anoutsole that makes up part of an article of footwear; a Co-extruded orLaminated Film Sampling Procedure, when the component is part of alayered film; a Neat Film Sampling Procedure, when the component is onlya film of the hydrogel; or a Neat Material Sampling Procedure, when thecomponent is a material available in a form other than a film. Each ofthese sampling procedures are described in more detail below.

(A)—Component Sampling Procedure

This procedure can be used to obtain a sample of the hydrogel when thehydrogel is incorporated as the first layer in an outsole component oras the external layer in an outsole of an article of footwear (e.g.,bonded to backing materials such as second polymeric material and/orthird polymeric material). An outsole sample, which includes thehydrogel in a non-wet state (e.g., at about 25 degrees C. and about 20percent relative humidity) is obtained as formed into an outsolecomponent or cut from the article of footwear using a blade. Thisprocess is performed by separating the outsole component from anassociated footwear upper, if present, and removing any materials fromthe article's top surface (e.g., corresponding to the top surface) thatcan uptake water and potentially skew the water uptake measurements ofthe hydrogel. For example, the article's top surface can be skinned,abraded, scraped, or otherwise cleaned to remove any upper adhesives,yarns, fibers, foams, and the like that could potentially take up waterthemselves.

The resulting outsole component sample includes the hydrogel and anyarticle substrate bonded to the hydrogel, and maintains the interfacialbond between the hydrogel and the associated backing materials of thefinished article. As such, any test using a Component Sampling Procedurecan simulate how the hydrogel will perform as part of an article offootwear. Additionally, this type of sample is also useful in caseswhere the interfacial bond between the hydrogel and the backingmaterials is less defined, such as where the hydrogel of the outsole ishighly diffused into the backing materials of the finished article(e.g., with a concentration gradient).

In this procedure, the sample is taken at a location along the outsolecomponent that provides a substantially constant thickness for thecomponent (within plus or minus 10 percent of the average thickness),such as in a forefoot region, mid-foot region, or a heel region of thearticle, and has a surface area of about 4.0 square centimeters (cm²).In cases where the hydrogel is not present on the outsole component inany segment having a 4.0 cm² surface area and/or where the thickness isnot substantially constant for a segment having a 4.0 cm² surface area,sample sizes with smaller cross-sectional surface areas can be taken andthe area-specific measurements are adjusted accordingly.

(B)—Co-Extruded or Laminated Film Sampling Procedure

This procedure can be used to obtain a sample of hydrogel of the presentdisclosure when the hydrogel is co-extruded with or laminated onto abacking substrate (e.g., third polymeric material) to form all or partof the layered film such as the film component used in an outsole of thepresent disclosure. The backing substrate represents a thermoplasticmaterial that is compatible with the composition of the hydrogel.

In some cases, the samples taken from co-extruded films are suitablesubstitutes to samples taken directly from outsoles or articles offootwear. Additionally, this sample is also useful in cases where theinterfacial bond between the hydrogel and a backing substrate is lessdefined, such as where the material is highly diffused into thecomposition of the backing substrate (e.g., with a concentrationgradient).

In this case, the hydrogel is co-extruded or laminated with the backingsubstrate as a web or sheet having a substantially constant thicknessfor the material (within plus or minus 10 percent of the averagematerial thickness), and cooled to solidify the resulting web or sheet.A sample of the hydrogel secured to the backing substrate is then cutfrom the resulting web or sheet, with a sample size surface area of 4cm², such that the material of the resulting sample remains secured tothe backing substrate.

(C)—Neat Film Sampling Procedure

This procedure can be used to obtain a sample of hydrogel of the presentdisclosure when the hydrogel is isolated in a neat form (i.e., withoutany bonded substrate in a layered film). In this case, the hydrogel isextruded as a web or sheet having a substantially constant materialthickness for the hydrogel (within plus or minus 10 percent of theaverage material thickness), and cooled to solidify the resulting web orsheet. A sample of the hydrogel having a surface area of 4 cm² is thencut from the resulting web or sheet.

Alternatively, if a source of the hydrogel is not available in a neatform, the material can be cut from an outsole substrate of a footwearoutsole, or from a backing substrate of a co-extruded sheet or web,thereby isolating the material. In either case, a sample of the materialhaving a surface area of 4 cm² is then cut from the resulting isolatedhydrogel.

(D)—Neat Material Sampling Procedure

This procedure can be used to obtain a sample of a material of thepresent disclosure. In this case, the material is provided in neat form,such as flakes, granules, powders, pellets, and the like. If a source ofthe material is not available in a neat form, the material can be cut,scraped, or ground from an outsole of a footwear outsole or from abacking substrate of a co-extruded sheet or web, thereby isolating thematerial.

Example 2—Test Protocols

The following test procedures are described with reference to outsolescomponents used in articles of footwear according to the ComponentSampling Procedure. However, the same tests can be applied to samplesused in a simulated environment (e.g., using a sample prepared accordingto the Co-extruded or Laminated Film Sampling Procedure, the Neat FilmSampling Procedure or the Neat Material Sampling Procedure). In otherwords, a measurement obtained on a neat material can be attributed to anoutsole comprising the material where the material defines at least aportion of a surface or side of the outsole. Additionally, a measurementmade in a simulated environment can be used to select the desiredperformance property for an outsole comprising the material where thematerial defines at least a portion of a surface or side of the outsole.

(I)—Water Uptake Capacity Test Protocol

This test measures the water uptake capacity of the hydrogel after apredetermined soaking duration for a sample (e.g., taken with theabove-discussed Component Sampling Procedure). The sample is initiallydried at 60° C. until there is no weight change for consecutivemeasurement intervals of at least 30 minutes apart (e.g., a 24-hourdrying period at 60 degrees C. is typically a suitable duration). Thetotal weight of the dried sample (Wt,_(sample dry)) is then measured ingrams. The dried sample is allowed to cool down to 25 degrees C., and isfully immersed in a deionized water bath maintained at 25 degrees C.After a given soaking duration, the sample is removed from the deionizedwater bath, blotted with a cloth to remove surface water, and the totalweight of the soaked sample (Wt,_(sample wet)) is measured in grams.

Any suitable soaking duration can be used, where a 24-hour soakingduration is believed to simulate saturation conditions for thethermoplastic hydrogel of the present disclosure (i.e., the hydrophilicthermoplastic hydrogel will be in its saturated state). Accordingly, asused herein, the expression “having a water uptake capacity at 5minutes” refers to a soaking duration of 5 minutes, the expression“having a water uptake capacity at 1 hour” refers to a soaking durationof 1 hour, the expression “having a water uptake capacity at 24 hours”refers to a soaking duration of 24 hours, and the like.

As can be appreciated, the total weight of a sample taken pursuant tothe Component Sampling Procedure includes the weight of the material asdried or soaked (Wt,_(sample dry) or Wt,_(sample wet)) and the weight ofthe backing material substrate (Wt,_(substrate)) needs to be subtractedfrom the sample measurements.

The weight of the substrate (Wt,_(substrate)) is calculated using thesample surface area (e.g., 4.0 cm²), an average measured thickness ofthe backing substrate in the sample, and the average density of thebacking substrate material. Alternatively, if the density of thematerial for the backing substrate is not known or obtainable, theweight of the substrate (Wt,_(substrate)) is determined by taking asecond sample using the same sampling procedure as used for the primarysample, and having the same dimensions (surface area and film/substratethicknesses) as the primary sample. The material of the second sample isthen cut apart from the substrate of the second sample with a blade toprovide an isolated substrate. The isolated substrate is then dried at60 degrees C. for 24 hours, which can be performed at the same time asthe primary sample drying. The weight of the isolated backing substrate(Wt,_(substrate)) is then measured in grams.

The resulting backing substrate weight (Wt,_(substrate)) is thensubtracted from the weights of the dried and soaked primary sample(Wt,_(sample dry) or Wt,_(sample wet)) to provide the weights of thematerial as dried and soaked (Wt,_(component dry) orWt,_(component wet)) as depicted by Equations 1 and 2.

Wt_(component dry)=Wt,_(sample dry)−Wt,_(substrate)  (Eq. 1)

Wt_(component wet)=Wt,_(sample wet)−Wt,_(substrate)  (Eq. 2)

The weight of the dried component (Wt._(component dry)) is thensubtracted from the weight of the soaked component (Wt_(component wet))to provide the weight of water that was taken up by the component, whichis then divided by the weight of the dried component(Wt._(component dry)) to provide the water uptake capacity for the givensoaking duration as a percentage, as depicted below by Equation 3.

$\begin{matrix}{{{Water}\mspace{14mu} {Uptake}\mspace{14mu} {Capacity}} = {\frac{{Wt}_{{component}\mspace{14mu} {wet}} - {Wt}_{{\cdot {component}}\mspace{14mu} {dry}}}{{Wt}_{{\cdot {component}}\mspace{14mu} {dry}}}\mspace{14mu} ( {100\%} )}} & ( {{Eq}.\mspace{14mu} 3} )\end{matrix}$

For example, a water uptake capacity of 50 percent at 1 hour means thatthe soaked component weighed 1.5 times more than its dry-state weightafter soaking for 1 hour. Similarly, a water uptake capacity of 500percent at 24 hours means that the soaked component weighed six timesmore than its dry-state weight after soaking for 24 hours.

(II)—Water Uptake Rate Test Protocol

This test measures the water uptake rate of the hydrogel by modelingweight gain as a function of soaking time for a sample with aone-dimensional diffusion model. The sample can be taken with any of theabove-discussed sampling procedures, including the Component SamplingProcedure. The sample is dried at 60 degrees C. until there is no weightchange for consecutive measurement intervals of at least 30 minutesapart (a 24-hour drying period at 60 degrees C. is typically a suitableduration). The total weight of the dried sample (Wt,_(sample dry)) isthen measured in grams. Additionally, the average thickness of thecomponent for the dried sample is measured for use in calculating thewater uptake rate, as explained below.

The dried sample is allowed to cool down to 25 degrees C., and is fullyimmersed in a deionized water bath maintained at 25 degrees C. Betweensoaking durations of 1, 2, 4, 9, 16, and 25 minutes, the sample isremoved from the deionized water bath, blotted with a cloth to removesurface water, and the total weight of the soaked sample(W,_(sample wet)) is measured, where “t” refers to the particularsoaking-duration data point (e.g., 1, 2, 4, 9, 16, or 25 minutes).

The exposed surface area of the soaked sample is also measured withcalipers for determining the specific weight gain, as explained below.The exposed surface area refers to the surface area that comes intocontact with the deionized water when fully immersed in the bath. Forsamples obtained using the Component Sampling Procedure, the samplesonly have one major surface exposed. For convenience, the surface areasof the peripheral edges of the sample are ignored due to theirrelatively small dimensions.

The measured sample is fully immersed back in the deionized water bathbetween measurements. The 1, 2, 4, 9, 16, and 25 minute durations referto cumulative soaking durations while the sample is fully immersed inthe deionized water bath (i.e., after the first minute of soaking andfirst measurement, the sample is returned to the bath for one moreminute of soaking before measuring at the 2-minute mark).

As discussed above in the Water Uptake Capacity Test, the total weightof a sample taken pursuant to the Component Sampling Procedure includesthe weight of the material as dried or soaked (Wt_(component wet) orWt._(component dry)) and the weight of the article or backing substrate(Wt,_(substrate)). In order to determine a weight change of the materialdue to water uptake, the weight of the backing substrate(Wt,_(substrate)) needs to be subtracted from the sample weightmeasurements. This can be accomplished using the same steps discussedabove in the Water Uptake Capacity Test to provide the resultingmaterial weights Wt,_(component wet) and Wt._(component dry) for eachsoaking-duration measurement.

The specific weight gain (Ws_(t)) from water uptake for each soakedsample is then calculated as the difference between the weight of thesoaked sample (Wt_(component wet)) and the weight of the initial driedsample (Wt._(component city)) where the resulting difference is thendivided by the exposed surface area of the soaked sample (A_(t)) asdepicted in Equation 4.

$\begin{matrix}{( {Ws}_{t} ) = \frac{( {{Wt}_{{component}\mspace{14mu} {wet}} - {Wt}_{{\cdot {component}}\mspace{14mu} {dry}}} )}{( A_{t} )}} & ( {{Eq}.\mspace{14mu} 4} )\end{matrix}$

where t refers to the particular soaking-duration data point (e.g., 1,2, 4, 9, 16, or 25 minutes), as mentioned above.

The water uptake rate for the hydrogel is then determined as the slopeof the specific weight gains (Ws_(t)) versus the square root of time (inminutes), as determined by a least squares linear regression of the datapoints. For the hydrogel of the present disclosure, the plot of thespecific weight gains (Ws_(t)) versus the square root of time (inminutes) provides an initial slope that is substantially linear (toprovide the water uptake rate by the linear regression analysis).However, after a period of time depending on the thickness of thecomponent, the specific weight gains will slow down, indicating areduction in the water uptake rate, until the saturated state isreached. This is believed to be due to the water being sufficientlydiffused throughout the hydrogel as the water uptake approachessaturation, and will vary depending on component thickness.

As such, for the component having an average thickness (as measuredabove) less than 0.3 millimeters, only the specific weight gain datapoints at 1, 2, 4, and 9 minutes are used in the linear regressionanalysis. In these cases, the data points at 16 and 25 minutes can beginto significantly diverge from the linear slope due to the water uptakeapproaching saturation, and are omitted from the linear regressionanalysis. In comparison, for the component having an average driedthickness (as measured above) of 0.3 millimeters or more, the specificweight gain data points at 1, 2, 4, 9, 16, and 25 minutes are used inthe linear regression analysis. The resulting slope defining the wateruptake rate for the sample has units of weight/(surface area-square rootof time), such as grams/(meter²-minutes^(1/2)) or g/m²/√min.

Furthermore, some component surfaces can create surface phenomenon thatquickly attract and retain water molecules (e.g., via surface hydrogenbonding or capillary action) without actually drawing the watermolecules into the film or substrate. Thus, samples of these films orsubstrates can show rapid specific weight gains for the 1-minute sample,and possibly for the 2-minute sample. After that, however, furtherweight gain is negligible. As such, the linear regression analysis isonly applied if the specific weight gain in data points at 1, 2, and 4minutes continue to show an increase in water uptake. If not, the wateruptake rate under this test methodology is considered to be about zerog/m²/√min.

(III)—Swelling Capacity Test Protocol

This test measures the swelling capacity of the component in terms ofincreases in thickness and volume after a given soaking duration for asample (e.g., taken with the above-discussed Component SamplingProcedure). The sample is initially dried at 60 degrees C. until thereis no weight change for consecutive measurement intervals of at least 30minutes apart (a 24-hour drying period is typically a suitableduration). The dimensions of the dried sample are then measured (e.g.,thickness, length, and width for a rectangular sample; thickness anddiameter for a circular sample, etc.). The dried sample is then fullyimmersed in a deionized water bath maintained at 25 degrees C. After agiven soaking duration, the sample is removed from the deionized waterbath, blotted with a cloth to remove surface water, and the samedimensions for the soaked sample are re-measured.

Any suitable soaking duration can be used. Accordingly, as used herein,the expression “having a swelling thickness (or volume) increase at 5minutes of.” refers to a soaking duration of 5 minutes, the expression“having a swelling thickness (or volume) increase at 1 hour of” refersto a test duration of 1 hour, the expression “having a swellingthickness (or volume) increase at 24 hours of” refers to a test durationof 24 hours, and the like.

The swelling of the component is determined by (1) an increase in thethickness between the dried and soaked component, by (2) an increase inthe volume between the dried and soaked component, or (3) both. Theincrease in thickness between the dried and soaked components iscalculated by subtracting the measured thickness of the initial driedcomponent from the measured thickness of the soaked component.Similarly, the increase in volume between the dried and soakedcomponents is calculated by subtracting the measured volume of theinitial dried component from the measured volume of the soakedcomponent. The increases in the thickness and volume can also berepresented as percentage increases relative to the dry thickness orvolume, respectively.

(IV)—Contact Angle Test

This test measures the contact angle of a sample surface (e.g., of asurface of an outsole of the present disclosure where the surface isdefined by the hydrogel of the present disclosure, or a surface of aco-extruded film formed of the hydrogel, or a surface of a neat filmformed of the hydrogel) based on a static sessile drop contact anglemeasurement for a sample (e.g., taken with the above-discussed ComponentSampling Procedure, Co-extruded or Laminated Film Sampling Procedure, orthe Neat Film Sampling Procedure). The contact angle refers to the angleat which a liquid interface meets the solid surface of the sample, andis an indicator of how hydrophilic the surface is.

For a dry test (i.e., to determine a dry-state contact angle), thesample is initially equilibrated at 25 degrees C. and 20 percenthumidity for 24 hours. For a wet test (i.e., to determine a wet-statecontact angle), the sample is fully immersed in a deionized water bathmaintained at 25 degrees C. for 24 hours. After that, the sample isremoved from the bath and blotted with a cloth to remove surface water,and clipped to a glass slide if needed to prevent curling.

The dry or wet sample is then placed on a moveable stage of a contactangle goniometer such as the goniometer commercially available under thetradename “RAME-HART F290” from Rame-Hart Instrument Co., Succasunna,N.J. A 10-microliter droplet of deionized water is then placed on thesample using a syringe and automated pump. An image is then immediatelytaken of the droplet (before material can take up the droplet), and thecontact angle of both edges of the water droplet are measured from theimage. The decrease in contact angle between the dried and wet samplesis calculated by subtracting the measured contact angle of the wetmaterial from the measured contact angle of the dry material.

(V)—Coefficient of Friction Test

This test measures the coefficient of friction of a sample surface(e.g., an outsole surface in accordance with the present disclosure, asurface of a co-extruded film formed of the hydrogel of the presentdisclosure, or a surface of a neat film formed of the hydrogel of thepresent disclosure) for a sample (e.g., taken with the above-discussedComponent Sampling Procedure, Co-extruded or Laminated Film SamplingProcedure, or the Neat Material Sampling Procedure). For a dry test(i.e., to determine a dry-state coefficient of friction), the sample isinitially equilibrated at 25 degrees C. and 20 percent humidity for 24hours. For a wet test (i.e., to determine a wet-state coefficient offriction), the sample is fully immersed in a deionized water bathmaintained at 25 degrees C. for 24 hours. After that, the sample isremoved from the bath and blotted with a cloth to remove surface water.

The measurement is performed with an aluminum sled mounted on analuminum test track, which is used to perform a sliding friction test onthe sample by sliding it on the aluminum surface of the test track. Thetest track measures 127 millimeters wide by 610 millimeters long. Thealuminum sled measures 76.2 millimeters×76.2 millimeters, with a 9.5millimeter radius cut into the leading edge. The contact area of thealuminum sled with the track is 76.2 millimeters×66.6 millimeters, or5,100 square millimeters).

The dry or wet sample is attached to the bottom of the sled using a roomtemperature-curing two-part epoxy adhesive commercially available underthe tradename “LOCTITE 608” from Henkel, Düsseldorf, Germany. Theadhesive is used to maintain the planarity of the wet sample, which cancurl when saturated. A polystyrene foam having a thickness of about 25.4millimeters is attached to the top surface of the sled (opposite of thetest sample) for structural support.

The sliding friction test is conducted using a screw-driven load frame.A tow cable is attached to the sled with a mount supported in thepolystyrene foam structural support, and is wrapped around a pulley todrag the sled across the aluminum test track. The sliding or frictionalforce is measured using a load transducer with a capacity of 2,000Newtons. The normal force is controlled by placing weights on top of thealuminum sled, supported by the polystyrene foam structural support, fora total sled weight of 20.9 kilograms (205 Newton). The crosshead of thetest frame is increased at a rate of 5 millimeters/second, and the totaltest displacement is 250 millimeters. The coefficient of friction iscalculated based on the steady-state force parallel to the direction ofmovement required to pull the sled at constant velocity. The coefficientof friction itself is found by dividing the steady-state pull force bythe applied normal force. Any transient value relating staticcoefficient of friction at the start of the test is ignored.

(VI)—Storage Modulus Test

This test measures the resistance of a sample of material (e.g.,hydrogel) to being deformed (ratio of stress to strain) when a vibratoryor oscillating force is applied to it, and is a good indicator of thehydrogel's compliance in the dry and wet states. For this test, a sampleis provided in film form using the Neat Film Sampling Procedure, whichis modified such that the surface area of the test sample is rectangularwith dimensions of 5.35 millimeters wide and 10 millimeters long. Thematerial thickness can range from 0.1 millimeters to 2 millimeters, andthe specific range is not particularly limited as the end modulus resultis normalized according to material thickness.

The storage modulus (E′) with units of megaPascals (MPa) of the sampleis determined by dynamic mechanical analysis (DMA) using a DMA analyzercommercially available under the tradename “Q800 DMA ANALYZER” from TAInstruments, New Castle, Del., which is equipped with a relativehumidity accessory to maintain the sample at constant temperature andrelative humidity during the analysis.

Initially, the thickness of the test sample is measured using calipers(for use in the modulus calculations). The test sample is then clampedinto the DMA analyzer, which is operated at the following stress/strainconditions during the analysis: isothermal temperature of 25 degrees C.,frequency of 1 Hertz, strain amplitude of 10 micrometers, preload of 1Newton, and force track of 125 percent. The DMA analysis is performed ata constant 25 degrees C. temperature according to the followingtime/relative humidity (RH) profile: (i) 0 percent RH for 300 minutes(representing the dry state for storage modulus determination), (ii) 50percent RH for 600 minutes, (iii) 90 percent RH for 600 minutes(representing the wet state for storage modulus determination), and (iv)0 percent RH for 600 minutes.

The E′ value (in MPa) is determined from the DMA curve according tostandard DMA techniques at the end of each time segment with a constantRH value. Namely, the E′ value at 0 percent RH (i.e., the dry-statestorage modulus) is the value at the end of step (i), the E′ value at 50percent RH is the value at the end of step (ii), and the E′ value at 90percent RH (i.e., the wet-state storage modulus) is the value at the endof step (iii) in the specified time/relative humidity profile.

The sample of the material can be characterized by its dry-state storagemodulus, its wet-state storage modulus, or the reduction in storagemodulus between the dry-state and wet-state materials, where wet-statestorage modulus is less than the dry-state storage modulus. Thisreduction in storage modulus can be listed as a difference between thedry-state storage modulus and the wet-state storage modulus, or as apercentage change relative to the dry-state storage modulus.

(VII)—Glass Transition Temperature Test

This glass transition temperature may be determined according to thetest method detailed in ASTM D3418-97 Standard Test Method forTransition Temperatures and Enthalpies of Fusion and Crystallization ofPolymers by Differential Scanning calorimetry, consistent with thedescription herein. This test measures the glass transition temperature(T_(g)) of a sample of the hydrogel, where the hydrogel is provided inneat form, such as with the Neat Film Sampling Procedure or the NeatMaterial Sampling Procedure, with a 10-milligram sample weight. Thesample is measured in both a dry state and a wet state (i.e., afterexposure to a humid environment as described herein).

The glass transition temperature is determined with DMA using a DMAanalyzer commercially available under the tradename “Q2000 DMA ANALYZER”from TA Instruments, New Castle, Del., which is equipped with aluminumhermetic pans with pinhole lids, and the sample chamber is purged with50 milliliters/minute of nitrogen gas during analysis. Samples in thedry state are prepared by holding at 0 percent RH until constant weight(less than 0.01 percent weight change over a 120 minute period). Samplesin the wet state are prepared by conditioning at a constant 25 degreesC. according to the following time/relative humidity (RH) profile: (i)250 minutes at 0 percent RH, (ii) 250 minutes at 50 percent RH, and(iii) 1,440 minutes at 90 percent RH. Step (iii) of the conditioningprogram can be terminated early if sample weight is measured duringconditioning and is measured to be substantially constant within 0.05percent during an interval of 100 minutes.

After the sample is prepared in either the dry or the wet state, it isanalyzed by Differential Scanning calorimetry (DSC) to provide a heatflow versus temperature curve. The DSC analysis is performed with thefollowing time/temperature profile: (i) equilibrate at −90 degrees C.for 2 minutes, (ii) ramp at +10 degrees C./minute to 250 degrees C.,(iii) ramp at −50 degrees C./minute to −90 degrees C., and (iv) ramp at+10 degrees C./minute to 250 degrees C. The glass transition temperaturevalue (in Celsius) is determined from the DSC curve according tostandard DSC techniques.

(VIII) Melt Flow Index Test.

The melt flow index is determined according to the test method detailedin ASTM D1238-13 Standard Test Method for Melt Flow Rates ofThermoplastics by Extrusion Plastometer, using Procedure A describedtherein. Briefly, the melt flow index measures the rate of extrusion ofthermoplastics through an orifice at a prescribed temperature and load.In the test method, approximately 7 grams of the material is loaded intothe barrel of the melt flow apparatus, which has been heated to atemperature specified for the material. A weight specified for thematerial is applied to a plunger and the molten material is forcedthrough the die. A timed extrudate is collected and weighed. Melt flowrate values are calculated in g/10 min.

(IX) Cold Ross Flex Test.

The cold Ross flex test is determined according the following testmethod. The purpose of this test is to evaluate the resistance tocracking of a sample under repeated flexing to 60 degrees in a coldenvironment. A thermoformed plaque of the material for testing is sizedto fit inside the flex tester machine. Each material is tested as fiveseparate samples. The flex tester machine is capable of flexing samplesto 60 degrees at a rate of 100+/−5 cycles per minute. The mandreldiameter of the machine is 10 millimeters. Suitable machines for thistest are the Emerson AR-6, the Satra S Tm 141F, the Gotech GT-7006, andthe Shin II Scientific SI-LTCO (DaeSung Scientific). The sample(s) areinserted into the machine according to the specific parameters of theflex machine used. The machine is placed in a freezer set to −6 degreesCelsius for the test. The motor is turned on to begin flexing with theflexing cycles counted until the sample cracks. Cracking of the samplemeans that the surface of the material is physically split. Visiblecreases of lines that do not actually penetrate the surface are notcracks. The sample is measured to a point where it has cracked but notyet broken in two.

(X) Modulus Test.

The modulus for a thermoformed plaque of material is determinedaccording to the test method detailed in ASTM D412-98 Standard TestMethods for Vulcanized Rubber and Thermoplastic Rubbers andThermoplastic Elastomers-Tension, with the following modifications. Thesample dimension is the ASTM D412-98 Die C, and the sample thicknessused is 2.0 millimeters+/−0.5 millimeters. The grip type used is apneumatic grip with a metal serrated grip face. The grip distance usedis 75 millimeters. The loading rate used is 500 millimeters/minute. Themodulus (initial) is calculated by taking the slope of the stress (MPa)versus the strain in the initial linear region.

Within this specification, embodiments have been described in a waywhich enables a clear and concise specification to be written, but it isintended and will be appreciated that embodiments can be variouslycombined or separated without parting from the invention. For example,it will be appreciated that all preferred features described herein areapplicable to all aspects of the invention described herein.

Additional aspects of the composition and properties of the hydrogelsincorporated into the outsoles used in forming articles of footwearherein, as well as additional aspects of other components used in thearticles of footwear and additional aspects of the associated testmethods and sampling procedures are described in International PatentPublication No.'s WO 2016/033276A1 (Int. Appl. No. PCT/US2015/047086);WO 2016/033274A1 (Int. Appl. No. PCT/US2015/047084); and WO2016/033271A1 (Int. Appl. No. PCT/US2015/047081). The entire contents ofeach of these patent publications are hereby incorporated by reference.

The foregoing description of various forms of the invention has beenpresented for purposes of illustration and description. It is notintended to be exhaustive or to limit the invention to the precise formsdisclosed. Numerous modifications or variations are possible in light ofthe above teachings. The forms discussed were chosen and described toprovide the best illustration of the principles of the invention and itspractical application to thereby enable one of ordinary skill in the artto utilize the invention in various forms and with various modificationsas are suited to the particular use contemplated. All such modificationsand variations are within the scope of the invention as determined bythe appended claims when interpreted in accordance with the breadth towhich they are fairly, legally, and equitably entitled.

The present disclosure can be described in accordance with the followingnumbered Clauses.

Clause 1. A method of manufacturing an outsole component for an articleof footwear, the method comprising:

providing a film component, the film component including a first layercompositionally comprising a polymeric hydrogel material, the firstlayer defining an externally-facing surface of the film component;

providing a mold having a molding surface;

placing the film component into the mold so that a portion of the firstlayer contacts a portion of the molding surface;

restraining the portion of the first layer against the portion of themolding surface while charging a second polymeric material into themold;

at least partially solidifying the charged second polymeric material inthe mold to produce the outsole component with the portion of the firstlayer of the film component forming an outermost layer of the outsolecomponent; and

removing the outsole component from the mold.

Clause 2. The method of manufacturing according to Clause 1, wherein thestep of providing the film component comprises providing a filmcomponent having a substantially planar geometry.

Clause 3. The method of manufacturing according to Clause 1 or 2,wherein the step of providing the film component comprises providing anextruded film component.

Clause 4. The method of manufacturing according to any of Clauses 1-3,wherein the step of providing the film component comprises providing afilm component comprising a layered film including a backing layeroperably connected to the first layer, the backing layer compositionallycomprising a third polymeric material.

Clause 5. The method of manufacturing according to any of Clauses 1-4,wherein the step of placing the film component into the mold so that aportion of the first layer contacts a portion of the molding surfacecomprises placing the film component into the mold so that the firstlayer contacts a portion of the molding surface which is less than 85%of a total molding surface area of the mold.

Clause 6. The method of manufacturing according to any of Clauses 1-5,wherein the method includes maintaining the film component at atemperature in a range of about 10 degrees Celsius (C) to about 80degrees C. except while charging the second polymeric material into themold, following charging the second polymeric material into the mold,and while at least partially solidifying the charged second polymericmaterial in the mold.

Clause 7. The method of manufacturing according to any of Clauses 1-6,wherein the step of providing the film component comprises providing thethird polymeric material;

providing the polymeric hydrogel material;

forming the layered film from the polymeric hydrogel material and thethird polymeric material using a co-extrusion process or a laminationprocess; and

cutting the layered film to form the film component.

Clause 8. The method of manufacturing according to any of Clauses 1-7,wherein the method further comprises providing a pre-formed tractionelement and adding the pre-formed traction element to the mold beforecharging the second polymeric material into the mold.

Clause 9. The method of manufacturing according to any of Clauses 1-8,wherein the method further comprises providing a pre-formed fitting fora traction element and adding the pre-formed fitting for a tractionelement to the mold before charging the second polymeric material intothe mold.

Clause 10. The method of manufacturing according to any one of Clauses1-9, wherein providing the film component comprises cutting a film toform the film component, wherein the film component is configured to fitbetween or around one or more traction elements.

Clause 11. The method of manufacturing according to Clause 9, whereinthe step of providing the film component comprises die cutting a filmusing a flatbed press or a rotary press to form the film component.

Clause 12. The method of manufacturing according to Clause 11, whereinthe step of die cutting uses a solid engraved die, an adjustable die,magnetic plate tooling, a dinking die, or a combination thereof.

Clause 13. The method of manufacturing according to any one of Clauses1-12, wherein the step of providing the film component comprisesconfiguring a portion of a film to fit between or around one or moretraction elements by cutting one or more holes in the portion of thefilm to accommodate the traction elements, or by shaping the portion ofthe film to avoid the one or more traction elements, or by both cuttingand shaping the film.

Clause 14. The method of manufacturing according to any of Clauses 1-13,wherein the second polymeric material is a thermoplastic polymericmaterial.

Clause 15. The method of manufacturing according to any of Clauses 1-14,wherein the third polymeric material is a thermoplastic polymericmaterial.

Clause 16. The method of manufacturing according to any of Clauses 1-15,wherein the step of charging the second polymeric material into the moldcomprises closing the mold and injecting the second polymeric materialinto the closed mold using an injection molding process.

Clause 17. The method of manufacturing according to any of Clauses 1-16,wherein charging the second polymeric material into the mold comprisescharging the second polymeric material into the mold, closing the moldbefore, during or after the charging, and applying compression to theclosed mold.

Clause 18. The method of manufacturing according to any of Clauses 1-17,wherein the step of restraining the first layer against the portion ofthe molding surface comprises using a vacuum, using one or moreretractable pins, or using both a vacuum and one or more retractablepins.

Clause 19. The method of manufacturing according to any of Clauses 1-18,wherein the molding surface is in the predetermined shape of thecomponent of the outsole.

Clause 20. The method of manufacturing the outsole according to any ofClauses 1-19, wherein at least a portion of the molding surface has apredetermined curvature.

Clause 21. The method of manufacturing according to any of Clauses 1-20,wherein placing the film component in the mold and/or restraining theportion of the first layer of the film component against the portion ofthe molding surface includes bending or curving the film component toconform to a curvature of the molding surface while maintaining the filmcomponent at a temperature in a range of about 10 degrees C. to about 80degrees C.

Clause 22. The method of manufacturing the outsole according to any ofClauses 1-21, wherein the second and third polymeric materials aresubstantially the same in composition.

Clause 23. The method of manufacturing the outsole according to any ofClauses 1-21, wherein the second and third polymeric materials aresubstantially different in composition from one another.

Clause 24. The method of manufacturing according to any of Clauses 1-23,wherein the one or more traction elements are integrally formed with theoutsole component during the molding step; separately added as snap-fitor screw-on components after the outsole is removed from the mold; or acombination thereof.

Clause 25. The method of manufacturing according to any of Clauses 1-24,where the one or more traction elements are integrally formed with theoutsole component using the second polymeric material.

Clause 26. The method of manufacturing according to any of Clauses 1-25,wherein the method further comprises adding a fourth polymeric materialinto the mold;

wherein the fourth polymeric material integrally forms the tractionelements as part of the outsole component.

Clause 27. The method of manufacturing according to Clause 26, whereinthe fourth polymeric material is a thermoplastic polymeric material.

Clause 28. The method of manufacturing according to any of Clauses 26 or27, wherein the fourth polymeric material is substantially the same incomposition as the second polymeric material.

Clause 29. The method of manufacturing according to any of Clauses 26 or27, wherein the fourth polymeric material has a greater level ofabrasion resistance than the second polymeric material.

Clause 30. The method of manufacturing according to any of Clauses 1-29,wherein the method further comprises placing one or more fittings intothe mold prior to adding the second polymeric material;

wherein the one or more fittings are configured to couple with thesnap-fit or screw-on components.

Clause 31. The method of manufacturing according to any of Clauses 1-30,wherein the method further comprises placing one or more preformedtraction element tips into the mold prior to adding the second polymericmaterial.

Clause 32. The method of manufacturing according to any of Clauses 30 or31, wherein the snap-fit or screw-on components comprise a material thatis different in composition from the second polymeric material.

Clause 33. The method of manufacturing according to any of Clauses 1-33,wherein the outsole component comprises traction elements, and thetraction elements are lugs, cleats, studs, spikes, or a combinationthereof.

Clause 34 The method of manufacturing according to any of Clauses 1-33,wherein the outsole component has a water uptake capacity at 1 hour ofgreater than 40 percent by weight as characterized by the Water UptakeCapacity Test with the Component Sampling Procedure.

Clause 35. The method of manufacturing according to any of Clauses 1-34,wherein the outsole component has a water uptake rate greater than 20g/m²/√min as characterized by the Water Uptake Rate Test with theComponent Sampling Procedure.

Clause 36. The method of manufacturing according to any of Clauses 1-35,wherein the outsole component has a swell thickness increase at 1 hourgreater than 20 percent as characterized by the Swelling Capacity Testwith the Component Sampling Procedure.

Clause 37. The method of manufacturing according to any of Clauses 1-36,wherein at least a portion of the external surface of the outsolecomponent exhibits one or more of a wet-state contact angle less than80° as characterized by the Contact Angle Test and a wet-statecoefficient of friction less than 0.8 as characterized by theCoefficient of Friction Test, with the Component Sampling Procedure.

Clause 38. The method of manufacturing according to any of Clauses 1-37,wherein the polymeric hydrogel material exhibits a wet-state glasstransition temperature equilibrated at 90 percent relative humidity anda dry-state glass transition temperature equilibrated at 0 percentrelative humidity, as characterized by the Glass Transition TemperatureTest with the Neat Material Sampling Process;

wherein the wet state glass transition temperature is more than 6degrees C. lower than the dry-state glass transition temperature.

Clause 39. The method of manufacturing according to any of Clauses 1-38,wherein the polymeric hydrogel material has a wet-state storage moduluswhen equilibrated at 90 percent relative humidity and a dry-statestorage modulus when equilibrated at 0 percent relative humidity, ascharacterized by the Storage Modulus Test with the Neat MaterialSampling Procedure;

wherein the wet-state storage modulus is less than the dry-state storagemodulus of the polymeric hydrogel material.

Clause 40. The method of manufacturing according to any of Clauses 1-39,wherein the polymeric hydrogel material is a thermoplastic hydrogelmaterial.

Clause 41. The method of manufacturing according to any of Clauses 1-40,wherein the polymeric hydrogel material comprises one or more polymersselected from a polyurethane, a polyamide homopolymer, a polyamidecopolymer, and any combination thereof.

Clause 42. The method of manufacturing according to any of Clauses 1-41,wherein the polymeric hydrogel material comprises a polyurethane.

Clause 43. The method of manufacturing according to Clause 42, whereinthe polyurethane is a thermoplastic polyurethane.

Clause 44. The method of manufacturing according to any of Clauses 1-43,wherein the polymeric hydrogel material comprises a polyamide blockcopolymer.

Clause 45. The method of manufacturing according to any of Clauses 1-44,wherein the polymeric hydrogel material comprises at least 80% of anexternal surface of the outsole component.

Clause 46. The method of manufacturing according to any of Clauses 1-45,wherein the polymeric hydrogel material has a dry-state thicknessranging from 0.1 millimeters (mm) to 2 mm.

Clause 47. The method of manufacturing according to any of Clauses 1-46,wherein at least one of the second polymeric material and the thirdpolymeric material comprises one or more natural or synthetic rubbers.

Clause 48. The method of manufacturing according to any of Clauses 1-47,wherein the second polymeric material and/or the third polymericmaterial further comprises one or more processing aids.

Clause 49. The method of manufacturing according to Clause 48, whereinthe processing aids are independently selected from the group of curingagents, initiators, plasticizers, mold release agents, lubricants,antioxidants, flame retardants, dyes, pigments, reinforcing andnon-reinforcing fillers, fiber reinforcements, and light stabilizers.

Clause 50. The method of manufacturing according to any of Clauses 1-49,wherein the step of at least partially solidifying the second polymericmaterial comprises at least partially crosslinking the second polymericmaterial.

Clause 51. The method of manufacturing according to Clause 50, whereinthe step of at least partially crosslinking the second polymericmaterial comprises at least partially crosslinking the second polymericmaterial using a sulfur-based crosslinking process, or aperoxide-initiated crosslinking process.

Clause 52. The method of manufacturing according to Clause 51, whereinthe cross-linking mechanisms occur upon exposure of the first polymericmaterial and/or second polymeric materials to actinic radiation at aconcentration and for a duration of time sufficient to at leastpartially cure the first and/or second polymeric materials.

Clause 53. The method of manufacturing according to any of Clauses 1-52,wherein the first polymeric material and/or second polymeric material isfully cured.

Clause 54. An outsole component manufactured according to the method ofany of Clauses 1-53.

Clause 55. A method of manufacturing an article of footwear, the methodcomprising:

providing an outsole component manufactured according to any of theClauses 1-53;

providing an upper; and

securing the outsole component and the upper to each other, such thatthe polymeric hydrogel material of the outsole component defines aground-facing surface of the article of footwear.

Clause 56. The method according to Clause 55, wherein the method furthercomprises:

receiving a midsole; and

attaching the midsole to the outsole component and/or the upper prior tosecuring the outsole component to the upper, such that the midsoleresides between the outsole component and the upper.

Clause 57. The method according to any of Clauses 55 or 56, wherein theupper comprises, leather, a thermoset polymer, a thermoplastic polymer,or a mixture thereof.

Clause 58. The method according to any of Clauses 55-57, wherein theupper comprises a textile selected as one from a knit textile, a woventextile, a non-woven textile, a braided textile, or a combinationthereof.

Clause 59. The method according to Clause 58, wherein the textileincludes one or more natural or synthetic fibers or yarns.

Clause 60. The method according to Clause 59, wherein the syntheticfibers or yarns comprise a thermoplastic polyurethane (TPU), apolyamide, a polyester, a polyolefin, or a mixture thereof.

Clause 61. The method according to any of Clauses 55-60, whereinsecuring the outsole component to the upper includes the use of anadhesive, a primer, or a combination thereof.

Clause 62. An outsole for use in an article of footwear comprising anoutsole component manufactured according to any of Clauses 1-54.

Clause 63. The use of the outsole component formed according to themethod of any of Clauses 1-54 in the article of footwear.

Clause 64. The article of footwear manufactured according to any ofClauses 55-61.

Clause 65. The use of an article of footwear formed according to themethod of any of Clauses 55-61.

Clause 66. An outsole component for an article of footwear, the outsolecomponent comprising:

a film component, the film component having a first surface, a secondsurface opposite the ground-contacting surface, and an externalperimeter, the film component compositionally comprising a polymerichydrogel material, the polymeric hydrogel material defining the firstsurface of the film component, and at least a portion of the firstsurface of the film component providing at least a portion of aground-contacting surface of the outsole component;

a second polymeric material operably connected to the second surface ofthe film component and to the entire external perimeter of each of theone or more film components; and

one or more traction elements;

wherein the film component fits between or around the one or moretraction elements.

Clause 67. The outsole component according to Clause 66, wherein theoutsole component comprises one or more traction elements, the one ormore traction elements having a ground-contacting surface, and theground-contacting surface of the one or more traction elements does notinclude the film component.

Clause 68. The outsole component according to Clause 66 or 67, whereinthe film component has a void having an interior perimeter, and thetraction element passes through the void of the film component.

Clause 69. The outsole component according to any of Clauses 66-68,wherein the traction element comprises the second polymeric material,and the second polymeric material is operably connected to the interiorperimeter of the film component.

Clause 70. The outsole component according to any of Clauses 66-69,wherein the second polymeric material defines the ground-contactingsurface of the traction element.

What is claimed is:
 1. A method of manufacturing an outsole componentfor an article of footwear, the method comprising: providing a moldhaving a molding surface; placing a film component into the mold,wherein the film component comprises a first externally-facing surface,the film component including a first layer compositionally comprising apolymeric hydrogel material, the first layer defining at least a portionof the first externally-facing surface of the film component;restraining the film component so that at least a portion of the firstlayer is in contact with the molding surface, forming a restrained filmcomponent; charging a second polymeric material into the mold with therestrained film component; at least partially solidifying the chargedsecond polymeric material in the mold to produce an outsole componentwith an outermost surface comprising at least a portion of the firstlayer of the film component; and removing the outsole component from themold.
 2. The method of manufacturing according to claim 1, furthercomprising the step of extruding or co-extruding a film comprising thepolymeric hydrogel material.
 3. The method of manufacturing according toclaim 1, wherein the film component further comprises a backing layeroperably connected to the first layer, the backing layer compositionallycomprising a third polymeric material.
 4. The method of manufacturingaccording to any of claim 1, the film component is placed or restrainedin the mold so that less than 85 percent of a total molding surface areaof the mold is contacted by the film component.
 5. The method ofmanufacturing according to claim 1, wherein the method further comprisesmaintaining the film component at a temperature in a range of about 10degrees C. to about 80 degrees C. except during the steps of chargingthe second polymeric material into the mold, and at least partiallysolidifying the charged second polymeric material in the mold.
 6. Themethod of manufacturing according to claim 3, wherein the method furthercomprises: providing the third polymeric material; providing thepolymeric hydrogel material; forming a layered film comprising a firstlayer of polymeric hydrogel material and a backing layer comprising thethird polymeric material using a co-extrusion process or a laminationprocess; and cutting the layered film to form the film component.
 7. Themethod of manufacturing according to claim 1, wherein the method furthercomprises providing one or more traction elements that are formedintegrally with or operably coupled with the molded outsole component,or a combination thereof.
 8. The method of manufacturing according toclaim 7, wherein the method further comprises adding a pre-formedtraction element or pre-formed fitting for a traction element to themold before charging the second polymeric material into the mold.
 9. Themethod of manufacturing according to claim 7, wherein the film componentis configured to fit between or around the one or more tractionelements.
 10. The method of manufacturing according to claim 1, furthercomprising the step of die cutting a film using a flatbed press, arotary press, a solid engraved die, an adjustable die, magnetic platetooling, a dinking die, or a combination thereof, to form the filmcomponent.
 11. The method of manufacturing according to claim 7, furthercomprising the step of cutting one or more holes or voids in a portionof the film component that corresponds to the location of the one ormore traction elements, or by shaping a portion of the film component toavoid the location of one or more traction elements, or by both cuttingand shaping the film component.
 12. The method of manufacturingaccording to claim 1, wherein the second polymeric material is athermoplastic polymeric material.
 13. The method of manufacturingaccording to claim 3, wherein the third polymeric material is athermoplastic polymeric material.
 14. The method of manufacturingaccording to claim 1, wherein the step of restraining the first layeragainst the portion of the molding surface comprises using a vacuum,using one or more retractable pins, or using both a vacuum and one ormore retractable pins.
 15. The method of manufacturing according toclaim 1, wherein placing the film component in the mold and/orrestraining the portion of the first layer of the film component againstthe portion of the molding surface comprises bending or curving the filmcomponent to conform to a curvature of the molding surface whilemaintaining the film component at a temperature in a range of about 10degrees C. to about 80 degrees C.
 16. The method of manufacturingaccording to claim 1, wherein the polymeric hydrogel material comprisespolymers or copolymers of polyurethane, polyurea, polyester,polycarbonate, polyetheramide, addition polymers of ethylenicallyunsaturated monomers, and any combination thereof.
 17. An outsolecomponent for an article of footwear, the outsole component comprisingan outsole component manufactured according to claim
 1. 18. An outsolecomponent for an article of footwear, the outsole component comprising:a ground-contacting surface; at least one film component, the filmcomponent having a first surface, a second surface opposed to the firstsurface, and an external perimeter, the film component compositionallycomprising a polymeric hydrogel material, the polymeric hydrogelmaterial defining at least a portion of the first surface of the filmcomponent and at least a portion of the ground-contacting surface of theoutsole component; a second polymeric material operably connected to thesecond surface of the film component and to the entire externalperimeter of each of the one or more film components; and one or moretraction elements; wherein the at least one film component fits betweenor around the one or more traction elements.
 19. The outsole componentaccording to claim 18, wherein the one or more traction elementscomprise a ground-contacting surface, and the ground-contacting surfaceof the one or more traction elements does not comprise the polymerichydrogel material of the film component.
 20. An article of footwearcomprising the outsole component according to claim 18.